CN109096482A - Flame-proof polyol composition and preparation method thereof, application - Google Patents
Flame-proof polyol composition and preparation method thereof, application Download PDFInfo
- Publication number
- CN109096482A CN109096482A CN201810585374.2A CN201810585374A CN109096482A CN 109096482 A CN109096482 A CN 109096482A CN 201810585374 A CN201810585374 A CN 201810585374A CN 109096482 A CN109096482 A CN 109096482A
- Authority
- CN
- China
- Prior art keywords
- flame
- proof
- epoxy group
- polyol composition
- glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 150000003077 polyols Chemical class 0.000 title claims abstract description 58
- 229920005862 polyol Polymers 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000006260 foam Substances 0.000 claims abstract description 38
- 229920002635 polyurethane Polymers 0.000 claims abstract description 37
- 239000004814 polyurethane Substances 0.000 claims abstract description 37
- 125000003700 epoxy group Chemical group 0.000 claims abstract description 34
- -1 phosphorous small molecule Chemical class 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 25
- 229920000570 polyether Polymers 0.000 claims abstract description 24
- 229920003023 plastic Polymers 0.000 claims abstract description 23
- 239000004033 plastic Substances 0.000 claims abstract description 23
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 21
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 46
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 44
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 30
- 239000003085 diluting agent Substances 0.000 claims description 24
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 20
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 20
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- 150000002148 esters Chemical class 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000003822 epoxy resin Substances 0.000 claims description 14
- 229920000647 polyepoxide Polymers 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 12
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 12
- 235000021317 phosphate Nutrition 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 11
- 125000005702 oxyalkylene group Chemical group 0.000 claims description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims description 10
- 238000007259 addition reaction Methods 0.000 claims description 9
- 239000012948 isocyanate Substances 0.000 claims description 9
- 150000002513 isocyanates Chemical class 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 8
- 150000001336 alkenes Chemical class 0.000 claims description 8
- 229940106691 bisphenol a Drugs 0.000 claims description 8
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 claims description 8
- 239000004088 foaming agent Substances 0.000 claims description 7
- 150000008301 phosphite esters Chemical class 0.000 claims description 7
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920001451 polypropylene glycol Polymers 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 claims description 5
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- FOVKHTSFPJLUQN-UHFFFAOYSA-N 1-ethoxy-1,3,5-triazinane-2,4,6-trione Chemical class CCON1C(=O)NC(=O)NC1=O FOVKHTSFPJLUQN-UHFFFAOYSA-N 0.000 claims description 3
- MOBNLCPBAMKACS-UHFFFAOYSA-N 2-(1-chloroethyl)oxirane Chemical compound CC(Cl)C1CO1 MOBNLCPBAMKACS-UHFFFAOYSA-N 0.000 claims description 3
- YSUQLAYJZDEMOT-UHFFFAOYSA-N 2-(butoxymethyl)oxirane Chemical group CCCCOCC1CO1 YSUQLAYJZDEMOT-UHFFFAOYSA-N 0.000 claims description 3
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 claims description 3
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 claims description 3
- USDJGQLNFPZEON-UHFFFAOYSA-N [[4,6-bis(hydroxymethylamino)-1,3,5-triazin-2-yl]amino]methanol Chemical compound OCNC1=NC(NCO)=NC(NCO)=N1 USDJGQLNFPZEON-UHFFFAOYSA-N 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- 239000000539 dimer Substances 0.000 claims description 3
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 229940051250 hexylene glycol Drugs 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- RDBMUARQWLPMNW-UHFFFAOYSA-N phosphanylmethanol Chemical compound OCP RDBMUARQWLPMNW-UHFFFAOYSA-N 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229930185605 Bisphenol Natural products 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 235000009508 confectionery Nutrition 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- ZYUVGYBAPZYKSA-UHFFFAOYSA-N 5-(3-hydroxybutan-2-yl)-4-methylbenzene-1,3-diol Chemical compound CC(O)C(C)C1=CC(O)=CC(O)=C1C ZYUVGYBAPZYKSA-UHFFFAOYSA-N 0.000 claims 1
- NHADDZMCASKINP-HTRCEHHLSA-N decarboxydihydrocitrinin Natural products C1=C(O)C(C)=C2[C@H](C)[C@@H](C)OCC2=C1O NHADDZMCASKINP-HTRCEHHLSA-N 0.000 claims 1
- 150000005690 diesters Chemical class 0.000 claims 1
- 239000003063 flame retardant Substances 0.000 abstract description 38
- 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 abstract description 21
- 230000008569 process Effects 0.000 abstract description 5
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 description 18
- 229920005830 Polyurethane Foam Polymers 0.000 description 15
- 239000011496 polyurethane foam Substances 0.000 description 15
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 238000009413 insulation Methods 0.000 description 5
- LDTMPQQAWUMPKS-UHFFFAOYSA-N 1-chloro-3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=CCl LDTMPQQAWUMPKS-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012774 insulation material Substances 0.000 description 4
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 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 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006757 chemical reactions by type Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006261 foam material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000009421 internal insulation Methods 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 2
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- MPNNOLHYOHFJKL-UHFFFAOYSA-N peroxyphosphoric acid Chemical compound OOP(O)(O)=O MPNNOLHYOHFJKL-UHFFFAOYSA-N 0.000 description 2
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 2
- 230000000644 propagated effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 150000003512 tertiary amines Chemical group 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical compound FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 description 1
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 1
- VJGCZWVJDRIHNC-UHFFFAOYSA-N 1-fluoroprop-1-ene Chemical compound CC=CF VJGCZWVJDRIHNC-UHFFFAOYSA-N 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- QHWKHLYUUZGSCW-UHFFFAOYSA-N Tetrabromophthalic anhydride Chemical class BrC1=C(Br)C(Br)=C2C(=O)OC(=O)C2=C1Br QHWKHLYUUZGSCW-UHFFFAOYSA-N 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 230000008821 health effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- SNMVRZFUUCLYTO-UHFFFAOYSA-N n-propyl chloride Chemical compound CCCCl SNMVRZFUUCLYTO-UHFFFAOYSA-N 0.000 description 1
- DIVDFFZHCJEHGG-UHFFFAOYSA-N oxidopamine Chemical compound NCCC1=CC(O)=C(O)C=C1O DIVDFFZHCJEHGG-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- YKCZJIWYDFOONC-UHFFFAOYSA-N phosphanylmethanamine Chemical class NCP YKCZJIWYDFOONC-UHFFFAOYSA-N 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
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
- C08G18/48—Polyethers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
- C08G18/5075—Polyethers having heteroatoms other than oxygen having phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2110/00—Foam properties
- C08G2110/0025—Foam properties rigid
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
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- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
- C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
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- C08J2203/00—Foams characterized by the expanding agent
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- C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2375/04—Polyurethanes
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Abstract
The invention discloses one kind to form flame-proof polyol composition by the pure and mild polyether polyol of phosphorus contained multicomponent, and further discloses the weight fraction ratio of each polyalcohol；Wherein, phosphorus-containing polyol is by the way that phosphorous small molecule and epoxy group substance reaction are prepared phosphor-containing flame-proof polyalcohol, and the viscosity of phosphor-containing flame-proof polyalcohol is 1500-3500mpas, and hydroxyl value is in 400-600mg KOH/g；The hydroxyl of phosphorous small molecule and the molal quantity ratio of epoxy group substance epoxy group are 1:0.8 to 1:1.The invention also discloses the preparation method of above-mentioned flame-proof polyol composition and the applications in polyurethane rigid foam plastic.Ignition-proof element is introduced on the strand of polyurethane by the present invention by chemically reacting, and shows the stability in high flame retardant and application process, and developing low-cost, no coupling product, simple process and tool high flame resistance.
Description
Technical field
The present invention relates to polyurethane foam plastics technical field, a kind of flame-proof polyol composition and its system are specifically provided
Preparation Method, application.
Background technique
Polyurethane rigid foam plastic is that have the low-density micropore carbamate macromolecule for reacting and generating with isocyanates
Material, has that light, water absorption rate is low, heat-insulation and heat-preservation is good, weatherability is strong, thermal coefficient is low and preferable mechanical property and resistance to
The performances such as chemical attack are widely used in the heat preserving and insulating material of pipe insulation, refrigerating equipment and building etc..However, not
Fire retardant treated hard polyurethane foam oxygen index (OI) belongs to combustible material 18 or so；And it is released in combustion process a large amount of
Toxic gas (CO, NO, HCN etc.) and dense smoke have very big potential hazard to the life and health property safety of people.
With the continuous propulsion of national energy-saving environmental protection policy, the implementation of Regulation of building energy-saving, people do not require nothing more than polyurethane
Foam has good thermal insulation property, and the requirement to its flame retardant property also increasingly increases.
Currently, the fire-retardant of polyurethane heat insulation material has addition type and two kinds of response type, additive flame retardant refers in poly- ammonia
Additional fire retardant in ester thermal insulation material, the fire retardant exist with non-covalent bond, and in actual use, the amount of addition is larger, with answering
With the growth of time, which is readily migrate into surface, generates pollution to environment, cannot persistently keep flame retardant effect and break
Bad foam physics performance reduces the mechanical property of polyurethane material, therefore, prepares reaction-type flame-retarding polyurethane material as people
The hot spot paid close attention to.
Reaction-type flame-retarding polyalcohol is that ignition-proof element is introduced on the strand of polyurethane by chemically reacting, and is shown
Stability in high flame retardant and application process, flame-proof polyol such as three (polyoxygenated alkene) phosphite ester common at present,
Three (polyoxygenated alkene) phosphates, bromination pentaerythrite and tetrabromophthalic anhydride series polyalcohol, with polyether polyol, melamine,
The nitrogenous fire resistant polymer polylol that dicyandiamide, uric acid synthesize, the oligomer that phosphorus oxychloride, pentaerythrite, ethylenediamine synthesize
Expansion type flame-retarding polyalcohol etc..
But reactive flame retardant in the prior art it is fire-retardant it is at high cost, preparation process is complicated, flame retardant effect is general, grinds
Study carefully developing low-cost, no coupling product, the simple process and flame-proof polyol technology of preparing for having high flame resistance has important meaning
Justice.
Summary of the invention
It is an object of the present invention to making up the deficiencies in the prior art, the low in cost, simple process of one kind and tool are provided
There is the preparation method of the flame-proof polyol composition of high flame resistance.
Another object of the present invention is to provide the purposes of the flame-proof polyol composition, the flame-proof polyols, for making
Standby flame retardant polyurethane rigid foam plastics.
Embodiments of the present invention first is that disclose a kind of flame-proof polyol composition, the flame-proof polyol composition
It is made of the pure and mild polyether polyol of phosphorus contained multicomponent, the weight fraction ratio of each polyalcohol is as follows:
Wherein, the phosphorus-containing polyol is polynary by the way that phosphorous small molecule is prepared phosphor-containing flame-proof with epoxy group substance reaction
The viscosity of alcohol, the phosphor-containing flame-proof polyalcohol is 1500-3500 mpas, and hydroxyl value is in 400-600mg KOH/g；
Further, the hydroxyl of phosphorous small molecule and rubbing for epoxy group substance epoxy group in the phosphor-containing flame-proof polyalcohol
Your number ratio is 1:0.8 to 1:1.
As the further improvement of embodiment of the present invention, the phosphorous small molecule includes phosphate ester monomer, the phosphoric acid
Ester monomer is selected from dimethyl phosphate, diethyl phosphate, dibutylphosphoric acid ester, diphenyl phosphate, hydroxyl phosphate, O, O '-diethyl-
Bis- (2- hydroxyethyl) the AminomethylphosphoniAcid Acid esters of N, N-, three (a contracting propylene glycol) phosphates, three (dipropylene glycol) phosphite esters,
At least one of three (polyoxygenated alkene) phosphates, three (polyoxygenated alkene) phosphite esters, tetrakis hydroxymetyl phosphonium sulfuric.
As the further improvement of embodiment of the present invention, the epoxy group substance, including the resin with epoxy group
Or the diluent with epoxy group；
The resin with epoxy group is by epoxychloropropane or methyl epichlorohydrin and bisphenol-A, Bisphenol F or double
The epoxy resin that phenol sulfone reacts；
The diluent is poly epihydric alcohol of the epoxyalkane through the polyglycidyl ether of addition or polyalcohol of bisphenol-A
Ether or polycarboxylic poly glycidyl ester and poly epihydric alcohol amine；
Wherein, the polyalcohol includes polypropylene glycol, 1,6- hexylene glycol, trimethylolpropane or glycerol；
The polycarboxylic acid includes adipic acid, phthalic acid or dimer acid.
As the further improvement of embodiment of the present invention, the epoxy group substance includes bisphenol-A or Bisphenol F and epoxy chlorine
The epoxy resin of propane preparation and the mixture of reactive diluent；
The reactive diluent is single reactive diluent or double activated diluent；
The list reactive diluent is butyl glycidyl ether, phenyl glycidyl ether or C12-C13Glycidol ether；
The double activated diluent is the Polyethylene Glycol Bisglycidyl Ether that molecular weight is 200-400 or molecular weight is 200-
400 polypropylene glycol glycidol ether.
As the further improvement of present embodiment, the oxyalkylene includes ethylene oxide, propylene oxide, epoxy fourth
At least one of alkane.
As the further improvement of present embodiment, selected foaming agent is selected from common foaming agent, such as pentamethylene, isoamyl
At least one of the chloro- 3,3,3- trifluoro propene (LBA) of alkane, pentafluoropropene (245fa), 1-, hexafluorobutene (FEA-1100).
As the further improvement of present embodiment, the isocyanates is polymethylene multi-phenenyl isocyanate, institute
Stating isocyanate content is 30.5-32.0%, viscosity 150-250mPas.
As the further improvement of embodiment of the present invention, the polyether glycol I is nitrogenous polyalcohol, by nitrogenous starting
Agent and oxyalkylene are prepared by addition reaction；
Wherein, the nitrogenous initiator is selected from melamine, trimethylol melamine, three (2- ethoxy) isocyanuric acids
One of ester；The characteristic feature viscosity of the polyether glycol I I is 400-800mpas, and hydroxyl value is 250-500mg KOH/
g。
As the further improvement of embodiment of the present invention, the polyether glycol I I is selected from ethylene glycol, propylene glycol, a contracting
At least one of diethylene glycol, triethylene-glycol, neopentyl glycol, hexylene glycol pass through addition as initiator and oxyalkylene
Reaction preparation；The characteristic feature viscosity of the polyether glycol I I is 150-250mpas, and hydroxyl value is 160-300mg KOH/g,
Average functionality is 1-2.
As the further improvement of embodiment of the present invention, the polyether glycol I II is with glycerol, trimethylolpropane
At least one of be prepared as initiator and oxyalkylene by addition reaction；The typical case of the polyether glycol I II
Intrinsic viscosity is 400-800mpas, hydroxyl value 250-500mgKOH/g, average functionality 2-3.
Embodiments of the present invention second is that disclosing the preparation method of above-mentioned flame-proof polyol composition, the method packet
Include following steps:
Epoxy group substance is added in reaction kettle, keeps in reaction kettle 70-80 DEG C of reaction temperature；
Phosphorous small molecule is added dropwise, is added dropwise to complete after 0.5-1 hours, temperature of reaction kettle is increased to 90 DEG C, reaction 3-5 is small
When；
Reduce temperature of reaction kettle, discharging.
Embodiments of the present invention third is that disclosing above-mentioned flame-proof polyol composition or above-mentioned preparation method obtains
Flame-proof polyol composition preparing the application in polyurethane rigid foam plastic.
Wherein, each raw material weight number ratio of above-mentioned polyurethane rigid foam plastic is as follows:
The preparation method of above-mentioned polyurethane rigid foam plastic the following steps are included:
S1, by flame-proof polyol composition in 20-25 DEG C of mixing 2-3h, pre- white material is made；
S2, foaming agent is mixed into 2-3h under conditions of temperature is 20-25 DEG C, blend pressure is 2-3bar with pre- white material,
The first mixture is made；
S3, the first mixture and isocyanates are mixed under 20-25 DEG C, 120-140bar pressure, injection preheating 40-50
DEG C die cavity, is foamed and is cured；
S4, the foams cooled down are demoulded, is tested for the property.
In another aspect, another embodiment of the present invention is to disclose above-mentioned polyurethane rigid foam plastic or above-mentioned side
Purposes of the polyurethane rigid foam plastic of method preparation in household electrical appliances internal insulation material, in specific implementation, present invention institute is public
The polyurethane rigid foam plastic composite material opened can be used in refrigerator, refrigerator, solar energy, gas heater and disinfection cabinet household electrical appliances
Portion's heat preservation.
The invention has the following advantages:
1) compared with adding physical fire retardant, the polyalcohol containing ignition-proof element provided in this case is drawn by chemical method
Enter into polyol structure, avoid physical fire retardant bring migration problem, holding hard polyurethane foam that can be permanent has
There is good flame retardant property；And the mechanical property of polyurethane material will not be made to reduce；
2) it when the hard polyurethane foam of this method preparation is fire-retardant heated using phosphorous foam, is easy dehydration and generates strong acid
Phosphoric acid, while releasing vapor and taking away heat, and the fire retardant mechanism of blocking oxygen and foam contacting, while phosphoric acid can be carbonized bubble
Foam, barrier outside heat are propagated inside, play good flame retardant effect；
3) compared with fire retardant polyurethane foam is not added, foam flame retardant property of the embodiment of the present invention improves significantly；It is logical
The hard polyurethane foam that above-mentioned flame-proof polyol composition and the above method are prepared is crossed, viscosity low guaranteed hair is expected in combination
The good fluidity of foam material can be rapidly filled with mold；And the hard polyurethane foam thermal coefficient prepared is lower, comprehensive performance
Preferably；
4) embodiment of the present invention further discloses the flame-proof polyol composition with tertiary amine structure, to polyurethane
Reaction itself has corresponding catalytic, has more preferably flame retardant effect, oxygen index (OI) lower, same using phosphorus-nitrogen collaboration effect
When the polyurethane thermal coefficient for preparing it is lower, comprehensive performance is preferable；
5) the heated nitrogenous compound for being easy to decompose such as the melamine introduced in the embodiment of the present invention, is heated and generates ammonia
Gas, can blocking oxygen and foam contacting, while ammonia can expand carbon-coating, prevent heat and the inside transmitting of flame, thus
Improve the flame retardant effect of polyurethane.
6) the hard polyurethane foam intensity of preparation of the embodiment of the present invention is high, and thermal coefficient is low；Pass through this rigid polyurethane
The refrigerator of matter foam preparation has better intensity, better thermal insulation property.
Specific embodiment
To keep the purposes, technical schemes and advantages of the application clearer, below in conjunction with the application specific embodiment
Technical scheme is clearly and completely described.Obviously, described embodiment is only that the application a part is implemented
Mode, rather than whole embodiments.Based on the embodiment in the application, those of ordinary skill in the art are not being made
Every other embodiment obtained, shall fall in the protection scope of this application under the premise of creative work.
Embodiments of the present invention are described below in detail, embodiments described below is exemplary, and is only used for explaining
The present invention, and be not considered as limiting the invention.
Embodiments of the present invention first is that disclose a kind of flame-proof polyol composition, the flame-proof polyol composition by
The pure and mild polyether polyol composition of phosphorus contained multicomponent, the weight fraction ratio of each polyalcohol are as follows:
Wherein, the phosphorus-containing polyol is polynary by the way that phosphorous small molecule is prepared phosphor-containing flame-proof with epoxy group substance reaction
The viscosity of alcohol, the phosphor-containing flame-proof polyalcohol is 1500-3500mpas, and hydroxyl value is in 400-600mg KOH/g；
Further, in phosphor-containing flame-proof polyalcohol the hydroxyl of phosphorous small molecule and epoxy group substance epoxy group molal quantity
Ratio is 1:0.8 to 1:1.
As the further improvement of embodiment of the present invention, phosphorous small molecule includes phosphate ester monomer, phosphate ester monomer choosing
From dimethyl phosphate, diethyl phosphate, dibutylphosphoric acid ester, diphenyl phosphate, hydroxyl phosphate, O, O '-diethyl-N, N- is bis-
(2- hydroxyethyl) AminomethylphosphoniAcid Acid ester, three (a contracting propylene glycol) phosphates, three (dipropylene glycol) phosphite esters, three (gather
Oxyalkylene) phosphate, three (polyoxygenated alkene) phosphite esters, at least one of tetrakis hydroxymetyl phosphonium sulfuric.
As the further improvement of embodiment of the present invention, epoxy group substance, including with epoxy group resin or
Diluent with epoxy group；
Wherein, the resin with epoxy group be by epoxychloropropane or methyl epichlorohydrin and bisphenol-A, Bisphenol F or
The epoxy resin that bisphenol sulphone reacts；
Preferably, diluent is that the epoxyalkane of bisphenol-A is sweet through the bunching water of the polyglycidyl ether of addition or polyalcohol
Oily ether or polycarboxylic poly glycidyl ester and poly epihydric alcohol amine；
Above-mentioned polyalcohol includes polypropylene glycol, 1,6-HD, trimethylolpropane or glycerol；
Above-mentioned polycarboxylic acid includes adipic acid, phthalic acid or dimer acid.
As the further improvement of embodiment of the present invention, epoxy group substance can also include bisphenol-A or Bisphenol F and epoxy
The epoxy resin of chloropropane preparation, such as commercially viable production and E51, E20, E54, E44 for buying, the mixing with reactive diluent
Object；
Generally, reactive diluent is single reactive diluent or double activated diluent；
Preferably, single reactive diluent is butyl glycidyl ether, phenyl glycidyl ether or C12-C13Glycidol ether；
Optionally, double activated diluent is Polyethylene Glycol Bisglycidyl Ether that molecular weight is 200-400 or molecular weight is
The polypropylene glycol glycidol ether of 200-400.
As the further improvement of present embodiment, the oxyalkylene for participating in addition reaction is selected from ethylene oxide, epoxy third
At least one of alkane, epoxy butane.
As the further improvement of present embodiment, foaming agent is selected from common foaming agent, such as pentamethylene, isopentane, five
At least one of the chloro- 3,3,3- trifluoro propene (LBA) of fluoropropene (245fa), 1-, hexafluorobutene (FEA-1100).
As the further improvement of present embodiment, isocyanates is polymethylene multi-phenenyl isocyanate, the isocyanide
Acid and esters content is 30.5-32.0%, viscosity 150-250mPas.
As the further improvement of embodiment of the present invention, polyether glycol I be nitrogenous polyalcohol, by nitrogenous initiator with
Oxyalkylene is prepared by addition reaction；Nitrogen is also typical ignition-proof element, and the introducing of nitrogen can use nitrogen phosphorus association
It is incited somebody to action with fire-retardant
Wherein, the nitrogenous initiator is selected from melamine, trimethylol melamine, three (2- ethoxy) isocyanuric acids
One of ester；The characteristic feature viscosity of the polyether glycol I I is 400-800mpas, and hydroxyl value is 250-500mg KOH/
g。
As the further improvement of embodiment of the present invention, polyether glycol I I is selected from ethylene glycol, propylene glycol, a contracting diethyl
At least one of glycol, triethylene-glycol, neopentyl glycol, hexylene glycol pass through addition reaction as initiator and oxyalkylene
Preparation；The characteristic feature viscosity of the polyether glycol I I is 150-250mpas, and hydroxyl value is 160-300mg KOH/g, average
Degree of functionality is 1-2.
As the further improvement of embodiment of the present invention, polyether glycol I II is in glycerol, trimethylolpropane
At least one is prepared as initiator and oxyalkylene by addition reaction；The characteristic feature of the polyether glycol I II
Viscosity is 400-800mpas, and hydroxyl value is 250-500mg KOH/g, average functionality 2-3.
Embodiments of the present invention second is that disclose the preparation method of above-mentioned flame-proof polyol composition, specifically include with
Lower step:
Epoxy group substance is added in reaction kettle, keeps in reaction kettle 70-80 DEG C of reaction temperature；
Phosphorous small molecule is added dropwise, is added dropwise to complete after 0.5-1 hours, temperature of reaction kettle is increased to 90 DEG C, reaction 3-5 is small
When；
Reduce temperature of reaction kettle, discharging.
Embodiments of the present invention third is that disclosing above-mentioned flame-proof polyol composition or above-mentioned preparation method obtains
Flame-proof polyol composition preparing the application in polyurethane rigid foam plastic.
Wherein, each raw material weight number ratio of above-mentioned polyurethane rigid foam plastic is as follows:
The preparation method of above-mentioned polyurethane rigid foam plastic the following steps are included:
S1, by flame-proof polyol composition in 20-25 DEG C of mixing 2-3h, pre- white material is made；
S2, foaming agent is mixed into 2-3h under conditions of temperature is 20-25 DEG C, blend pressure is 2-3bar with pre- white material,
The first mixture is made；
S3, the first mixture and isocyanates are mixed under 20-25 DEG C, 120-140bar pressure, injection preheating 40-50
DEG C die cavity, is foamed and is cured；
S4, the foams cooled down are demoulded, is tested for the property.
In another aspect, another embodiment of the present invention is to disclose above-mentioned polyurethane rigid foam plastic or above-mentioned side
Purposes of the polyurethane rigid foam plastic of method preparation in household electrical appliances internal insulation material, in specific implementation, present invention institute is public
The polyurethane rigid foam plastic composite material opened can be used in refrigerator, refrigerator, solar energy, gas heater and disinfection cabinet household electrical appliances
Portion's heat preservation.
Specifically, in the present embodiment flame-proof polyol composition being related to and its polyurethane rigid foam plastic of preparation
The portion rate of raw material and additive specifically see the table below, the specific embodiment and in the prior art including different material and proportion composition
As a comparison case；
Embodiment 1
The phosphoric acid small molecule that the embodiment of the present invention is selected is diethyl phosphate, epoxy group substance is epoxy resin E51, molecule
The Polyethylene Glycol Bisglycidyl Ether that amount is 300；
The flame-proof polyol is the preparation method comprises the following steps: by 380g epoxy resin E51 and 300g polyethylene glycol glycidol
Ether is added in reaction kettle, then increases reaction temperature to 70 DEG C, 600g diethyl phosphate is added dropwise, and after 1 hour is added dropwise to complete, is risen
Temperature is reacted 4 hours, cooling discharge to 90 DEG C.
Prepared flame-proof polyol, viscosity is in 1500-2000mpa.s, hydroxyl value 550-600mgKOH/g.
Embodiment 2
The phosphoric acid small molecule that the embodiment of the present invention is selected is dibutylphosphoric acid ester, and epoxy group substance is epoxy resin E51, molecule
The Polyethylene Glycol Bisglycidyl Ether that amount is 200；
The flame-proof polyol is the preparation method comprises the following steps: by 380g epoxy resin E51 and 200g polyethylene glycol glycidol
Ether is added in reaction kettle, then increases reaction temperature to 70 DEG C, 800g diethyl phosphate is added dropwise, and after 1 hour is added dropwise to complete, is risen
Temperature is reacted 4 hours, cooling discharge to 90 DEG C.
Prepared flame-proof polyol, viscosity is in 1300-1600mpa.s, hydroxyl value 530-550mgKOH/g.
Embodiment 3
The phosphorous small molecule that the embodiment of the present invention is selected is O, bis- (2- hydroxyethyl) the aminomethyl phosphines of O`- diethyl-N, N-
The Polyethylene Glycol Bisglycidyl Ether that acid esters, epoxy group substance are epoxy resin E51, molecular weight is 200；
The flame-proof polyol is the preparation method comprises the following steps: by 380g epoxy resin E51 and 200g polyethylene glycol glycidol
Ether is added in reaction kettle, then increases reaction temperature to 70 DEG C, 1000gO, bis- (the 2- hydroxyl second of O`- diethyl-N, N- are added dropwise
Base) AminomethylphosphoniAcid Acid ester, after 1 hour is added dropwise to complete, 90 DEG C are warming up to, is reacted 5 hours, cooling discharge.
Prepared flame-proof polyol, viscosity is in 2100-2400mpa.s, hydroxyl value 460-490mgKOH/g.
Embodiment 4
The substance that the phosphorous small molecule that the embodiment of the present invention is selected is selected is diethyl phosphate and O, O`- diethyl-N, N-
Mixture, the epoxy group substance of bis- (2- hydroxyethyl) AminomethylphosphoniAcid Acid esters be epoxy resin E20, the poly- second that molecular weight is 200
Glycol glycidol ether；
The flame-proof polyol is the preparation method comprises the following steps: by 380g epoxy resin E51 and 200g polyethylene glycol glycidol
Ether is added in reaction kettle, then increases reaction temperature to 70 DEG C, 500gO, bis- (the 2- hydroxyl second of O`- diethyl-N, N- are added dropwise
Base) AminomethylphosphoniAcid Acid ester and 200g diethyl phosphate mixture, after 1 hour is added dropwise to complete, be warming up to 90 DEG C, react 5 hours,
Cooling discharge.
Prepared flame-proof polyol, viscosity is in 1800-2300mpa.s, hydroxyl value 480-530mgKOH/g.
The pure and mild polyether glycol I of phosphorus contained multicomponent that embodiment 1-4 is prepared, II, III are mixed to get jointly fire-retardant more
First alcohol composition is added separately to prepare polyurethane rigid foam plastic in embodiment 5-12, and with the comparative example of the prior art 1
The comparison of flame retardant property and mechanical performance is carried out with comparative example 2；Shown in table specific as follows:
The polyurethane rigid foam plastic that above-described embodiment is prepared carries out compressive strength, averag density, thermally conductive system
The performance test of number, low-temperature stability, rate of closed hole and oxygen index (OI)；Through the experimental results showed that, compared with the existing technology, the present invention is real
Example is applied by the way that phosphonium flame retardant is being added, has the oxygen index (OI) significantly improved, hence it is evident that improve flame retardant property.
Specifically, the beneficial effects of the present invention are:
1) compared with adding physical fire retardant, the polyalcohol containing ignition-proof element provided in this case is drawn by chemical method
Enter into polyol structure, avoid physical fire retardant bring migration problem, holding hard polyurethane foam that can be permanent has
There is good flame retardant property；And the mechanical property of polyurethane material will not be made to reduce；
2) it when the hard polyurethane foam of this method preparation is fire-retardant heated using phosphorous foam, is easy dehydration and generates strong acid
Phosphoric acid, while releasing vapor and taking away heat, and the fire retardant mechanism of blocking oxygen and foam contacting, while phosphoric acid can be carbonized bubble
Foam, barrier outside heat are propagated inside, play good flame retardant effect；
3) compared with fire retardant polyurethane foam is not added, foam flame retardant property of the embodiment of the present invention improves significantly；It is logical
The hard polyurethane foam that above-mentioned flame-proof polyol composition and the above method are prepared is crossed, viscosity low guaranteed hair is expected in combination
The good fluidity of foam material can be rapidly filled with mold；And the hard polyurethane foam thermal coefficient prepared is lower, comprehensive performance
Preferably；
4) embodiment of the present invention further discloses the flame-proof polyol composition with tertiary amine structure, to polyurethane
Reaction itself has corresponding catalytic, has more preferably flame retardant effect, oxygen index (OI) lower, same using phosphorus-nitrogen collaboration effect
When the polyurethane thermal coefficient for preparing it is lower, comprehensive performance is preferable；
5) the heated nitrogenous compound for being easy to decompose such as the melamine introduced in the embodiment of the present invention, is heated and generates ammonia
Gas, can blocking oxygen and foam contacting, while ammonia can expand carbon-coating, prevent heat and the inside transmitting of flame, thus
Improve the flame retardant effect of polyurethane.
6) the hard polyurethane foam intensity of preparation of the embodiment of the present invention is high, and thermal coefficient is low；Pass through this rigid polyurethane
The refrigerator of matter foam preparation has better intensity, better thermal insulation property.
It should be appreciated that although this specification is described in terms of embodiments, but not each embodiment only includes one
A independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should will say
As a whole, the technical solution in each embodiment may also be suitably combined to form those skilled in the art can for bright book
With the other embodiments of understanding.
The series of detailed descriptions listed above only for feasible embodiment of the invention specifically
Protection scope that is bright, being not intended to limit the invention, it is all without departing from equivalent implementations made by technical spirit of the present invention or change
More it should all be included in the protection scope of the present invention.
Claims (11)
1. a kind of flame-proof polyol composition, which is characterized in that the flame-proof polyol composition is by the pure and mild polyethers of phosphorus contained multicomponent
Polyalcohol composition, the weight fraction ratio of each polyalcohol are as follows:
The phosphorus-containing polyol be by the way that phosphorous small molecule and epoxy group substance reaction are prepared phosphor-containing flame-proof polyalcohol, it is described to contain
The viscosity of phosphorus flame-proof polyol is 1500-3500mpas, and hydroxyl value is in 400-600mgKOH/g；
The molal quantity ratio of the hydroxyl of phosphorous small molecule and epoxy group substance epoxy group is 1 in the phosphor-containing flame-proof polyalcohol:
0.8 to 1:1.
2. flame-proof polyol composition according to claim 1, which is characterized in that the phosphorous small molecule includes phosphate
Monomer, the phosphate ester monomer are selected from dimethyl phosphate, diethyl phosphate, dibutylphosphoric acid ester, diphenyl phosphate, di
Ester, O, bis- (2- hydroxyethyl) the AminomethylphosphoniAcid Acid esters of O '-diethyl-N, N-, three (a contracting propylene glycol) phosphates, a three (contractings two
Propylene glycol) phosphite ester, three (polyoxygenated alkene) phosphates, three (polyoxygenated alkene) phosphite esters, in tetrakis hydroxymetyl phosphonium sulfuric
It is at least one.
3. flame-proof polyol composition according to claim 1, which is characterized in that the epoxy group substance, including have
The resin of epoxy group or diluent with epoxy group；
The resin with epoxy group is by epoxychloropropane or methyl epichlorohydrin and bisphenol-A, Bisphenol F or bisphenol sulphone
React obtained epoxy resin；
The diluent is polyglycidyl ether of the epoxyalkane through the polyglycidyl ether of addition or polyalcohol of bisphenol-A, or
Polycarboxylic poly glycidyl ester and poly epihydric alcohol amine；
Wherein, the polyalcohol includes polypropylene glycol, 1,6- hexylene glycol, trimethylolpropane or glycerol；
The polycarboxylic acid includes adipic acid, phthalic acid or dimer acid.
4. flame-proof polyol composition according to claim 1 or 3, which is characterized in that the epoxy group substance includes double
The mixture of the epoxy resin and reactive diluent of phenol A or Bisphenol F and epoxychloropropane preparation；
The reactive diluent is single reactive diluent or double activated diluent；
The list reactive diluent is butyl glycidyl ether, phenyl glycidyl ether or C12-C13Glycidol ether；
The double activated diluent is the Polyethylene Glycol Bisglycidyl Ether that molecular weight is 200-400 or molecular weight is 200-400's
Polypropylene glycol glycidol ether.
5. flame-proof polyol composition according to claim 1, which is characterized in that the polyether glycol I is nitrogenous more
First alcohol is prepared by nitrogenous initiator and oxyalkylene by addition reaction；
Wherein, the nitrogenous initiator is in melamine, trimethylol melamine, three (2- ethoxy) isocyanuric acid esters
One kind；The characteristic feature viscosity of the polyether glycol I I is 400-800mpas, and hydroxyl value is 250-500mg KOH/g.
6. flame-proof polyol composition according to claim 1, which is characterized in that the polyether glycol I I is selected from second two
At least one of alcohol, propylene glycol, diglycol, triethylene-glycol, neopentyl glycol, hexylene glycol are used as initiator and oxygen
Change alkene to prepare by addition reaction；The characteristic feature viscosity of the polyether glycol I I is 150-250mpas, and hydroxyl value is
160-300mg KOH/g, average functionality 1-2.
7. flame-proof polyol composition according to claim 1, which is characterized in that the polyether glycol I II is with sweet
At least one of oil, trimethylolpropane are prepared as initiator and oxyalkylene by addition reaction；The polyethers
The characteristic feature viscosity of polyalcohol III is 400-800mpas, and hydroxyl value is 250-500mg KOH/g, average functionality 2-3.
8. a kind of method for preparing the described in any item flame-proof polyol compositions of claim 1-7, which is characterized in that the side
Method the following steps are included:
Epoxy group substance is added in reaction kettle, keeps in reaction kettle 70-80 DEG C of reaction temperature；
Phosphorous small molecule is added dropwise, is added dropwise to complete after 0.5-1 hours, temperature of reaction kettle is increased to 90 DEG C, is reacted 3-5 hours；
Reduce temperature of reaction kettle, discharging.
9. a kind of flame-proof polyol composition according to claim 1-7 or preparation side according to any one of claims 8
The flame-proof polyol composition that method obtains is preparing the application in polyurethane rigid foam plastic.
10. a kind of polyurethane rigid foam plastic according to claim 9, which is characterized in that the rigid poly urethanes bubble
The raw material weight number ratio of foam plastics is as follows:
11. a kind of method for preparing polyurethane rigid foam plastic described in any one of claim 10, which is characterized in that the method packet
Include following steps:
S1, by flame-proof polyol composition in 20-25 DEG C of mixing 2-3h, pre- white material is made；
S2, foaming agent is mixed into 2-3h under conditions of temperature is 20-25 DEG C, blend pressure is 2-3bar with pre- white material, be made
First mixture；
S3, the first mixture and isocyanates are mixed under 20-25 DEG C, 120-140bar pressure, injection 40-50 DEG C of mould of preheating
Chamber is foamed and is cured；
S4, the foams cooled down are demoulded, is tested for the property.
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| CN109796750A (en) * | 2018-12-29 | 2019-05-24 | 广州市聚科聚氨酯有限公司 | A kind of polyurethane rigid foam combined polyether |
| CN110092904A (en) * | 2019-05-31 | 2019-08-06 | 浙江枧洋高分子科技有限公司 | A kind of preparation method and application of polyether-modified phosphate polyalcohol |
| CN110669193A (en) * | 2019-09-04 | 2020-01-10 | 山西晋煤集团技术研究院有限责任公司 | Environment-friendly harmless high-flame-retardant polymer material for coal mine water plugging and coal rock reinforcing and preparation method thereof |
| CN111004379A (en) * | 2019-12-02 | 2020-04-14 | 浙江理工大学桐乡研究院有限公司 | Preparation method of flame-retardant polyol with high phosphorus content and multiple functionality degrees |
| CN113845640A (en) * | 2021-11-16 | 2021-12-28 | 万华化学集团股份有限公司 | Polyether polyol for polyurethane foam plastic and preparation method and application thereof |
| CN116948163A (en) * | 2023-09-20 | 2023-10-27 | 山东一诺威新材料有限公司 | Dihydroxyl DOPO halogen-free flame-retardant polyether polyol, and preparation method and application thereof |
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| CN116948163A (en) * | 2023-09-20 | 2023-10-27 | 山东一诺威新材料有限公司 | Dihydroxyl DOPO halogen-free flame-retardant polyether polyol, and preparation method and application thereof |
| CN116948163B (en) * | 2023-09-20 | 2023-12-29 | 山东一诺威新材料有限公司 | Dihydroxyl DOPO halogen-free flame-retardant polyether polyol, and preparation method and application thereof |
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