CN109096482B - 阻燃多元醇组合物及其制备方法、应用 - Google Patents
阻燃多元醇组合物及其制备方法、应用 Download PDFInfo
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- CN109096482B CN109096482B CN201810585374.2A CN201810585374A CN109096482B CN 109096482 B CN109096482 B CN 109096482B CN 201810585374 A CN201810585374 A CN 201810585374A CN 109096482 B CN109096482 B CN 109096482B
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- polyol
- flame
- phosphorus
- retardant
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- 229920005862 polyol Polymers 0.000 title claims abstract description 97
- 239000003063 flame retardant Substances 0.000 title claims abstract description 90
- -1 Flame-retardant polyol Chemical class 0.000 title claims abstract description 56
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- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 150000003077 polyols Chemical class 0.000 claims abstract description 48
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 42
- 239000011574 phosphorus Substances 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 27
- 229920000570 polyether Polymers 0.000 claims abstract description 27
- 239000000126 substance Substances 0.000 claims abstract description 22
- 239000004593 Epoxy Substances 0.000 claims abstract description 20
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000003085 diluting agent Substances 0.000 claims description 22
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 18
- 239000011496 polyurethane foam Substances 0.000 claims description 18
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 17
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 15
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- 239000007983 Tris buffer Substances 0.000 claims description 13
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- 229920001223 polyethylene glycol Polymers 0.000 claims description 11
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 10
- 230000000694 effects Effects 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 229910019142 PO4 Inorganic materials 0.000 claims description 9
- 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 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 claims description 8
- 239000012948 isocyanate Substances 0.000 claims description 8
- 150000002513 isocyanates Chemical class 0.000 claims description 8
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 7
- 229920000877 Melamine resin Polymers 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
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- JYFHYPJRHGVZDY-UHFFFAOYSA-N Dibutyl phosphate Chemical compound CCCCOP(O)(=O)OCCCC JYFHYPJRHGVZDY-UHFFFAOYSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
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- BPXVHIRIPLPOPT-UHFFFAOYSA-N 1,3,5-tris(2-hydroxyethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound OCCN1C(=O)N(CCO)C(=O)N(CCO)C1=O BPXVHIRIPLPOPT-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
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- 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
- 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
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims description 3
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
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- ZGTNBBQKHJMUBI-UHFFFAOYSA-N bis[tetrakis(hydroxymethyl)-lambda5-phosphanyl] sulfate Chemical compound OCP(CO)(CO)(CO)OS(=O)(=O)OP(CO)(CO)(CO)CO ZGTNBBQKHJMUBI-UHFFFAOYSA-N 0.000 claims 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 claims 1
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- 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 43
- 229920002635 polyurethane Polymers 0.000 abstract description 38
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- 239000000463 material Substances 0.000 description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 125000003700 epoxy group Chemical group 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 239000012774 insulation material Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 239000004604 Blowing Agent Substances 0.000 description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
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- 235000011187 glycerol Nutrition 0.000 description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 4
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- 230000002195 synergetic effect Effects 0.000 description 3
- 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 description 2
- 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
- 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 2
- MOBNLCPBAMKACS-UHFFFAOYSA-N 2-(1-chloroethyl)oxirane Chemical compound CC(Cl)C1CO1 MOBNLCPBAMKACS-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 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
- 239000000539 dimer Substances 0.000 description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 2
- 229940051250 hexylene glycol Drugs 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
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- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical class OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 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
- 150000003384 small molecules Chemical class 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 150000003512 tertiary amines Chemical group 0.000 description 2
- YIEDHPBKGZGLIK-UHFFFAOYSA-L tetrakis(hydroxymethyl)phosphanium;sulfate Chemical compound [O-]S([O-])(=O)=O.OC[P+](CO)(CO)CO.OC[P+](CO)(CO)CO YIEDHPBKGZGLIK-UHFFFAOYSA-L 0.000 description 2
- 230000002087 whitening effect Effects 0.000 description 2
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-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
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
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- 238000005057 refrigeration Methods 0.000 description 1
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- 229940116269 uric acid Drugs 0.000 description 1
Classifications
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- 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
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- 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
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- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4804—Two or more polyethers of different physical or chemical nature
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- 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
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- 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
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- 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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- 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
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- 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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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- 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
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- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
- C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
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- C—CHEMISTRY; METALLURGY
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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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- 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
- C08J2203/00—Foams characterized by the expanding agent
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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
- 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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Abstract
本发明公开了一种由含磷多元醇和聚醚多元醇组成阻燃多元醇组合物,并进一步公开了各多元醇的重量份数比;其中,含磷多元醇为通过将含磷小分子与环氧基物质反应制备含磷阻燃多元醇,含磷阻燃多元醇的粘度为1500‑3500mpa·s,羟值在400‑600mg KOH/g;含磷小分子的羟基与环氧基物质中环氧基的摩尔数比例为1:0.8至1:1。本发明还公开了上述阻燃多元醇组合物的制备方法以及在聚氨酯硬质泡沫塑料中的应用。本发明通过化学反应将阻燃元素引入到聚氨酯的分子链上,显示出高阻燃性以及应用过程中的稳定性,且开发低成本,无副产物,工艺简单且具高阻燃性能。
Description
技术领域
本发明涉及聚氨酯泡沫塑料技术领域,特别提供了一种阻燃多元醇组合物及其制备方法、应用。
背景技术
聚氨酯硬质泡沫塑料是有与异氰酸酯反应生成的低密度微孔氨基甲酸酯高分子材料,具有质轻、吸水率低、隔热保温性好、耐候性强、导热系数低以及较好的力学性能及耐化学腐蚀等性能,被广泛用于管道保温、冷藏设备以及建筑物等的保温隔热材料。然而,未经阻燃处理的聚氨酯硬质泡沫氧指数在18左右,属于易燃材料;且燃烧过程中释放出大量有毒气体(CO、NO、HCN等)及浓烟,对人们的生命健康财产安全具有很大的潜在危害。
随着国家节能环保政策的不断推进,建筑节能法规的实施,人们不仅要求聚氨酯泡沫具有良好的保温性能,对其阻燃性能的要求也日益增加。
目前,聚氨酯保温材料的阻燃有添加型和反应型两种,添加型阻燃剂是指在聚氨酯保温材料中外加阻燃剂,该阻燃剂以非共价键存在,在实际使用时,添加的量较大,随应用时间的增长,该类阻燃剂容易迁移到表面,对环境产生污染,不能持久保持阻燃效果和破坏泡沫物理性能、使聚氨酯材料的力学性能降低,因此,制备反应型阻燃聚氨酯材料成为人们关注的热点。
反应型阻燃多元醇是通过化学反应将阻燃元素引入到聚氨酯的分子链上,显示出高阻燃性以及应用过程中的稳定性,目前常见的阻燃多元醇如三(聚氧化烯烃)亚磷酸酯,三(聚氧化烯烃)磷酸酯,溴化季戊四醇及四溴苯酐系列多元醇,以聚醚多元醇、三聚氰胺、双氰胺、尿酸合成的含氮的阻燃聚合物多元醇,三氯氧磷、季戊四醇、乙二胺合成的低聚物膨胀型阻燃多元醇等等。
但是现有技术中的反应型阻燃剂的阻燃成本高、制备工艺复杂,阻燃效果一般,研究开发低成本,无副产物,工艺简单且具高阻燃性能的阻燃多元醇制备技术具有重要的意义。
发明内容
本发明的目的之一在于弥补现有技术的不足,提供一种成本低廉、工艺简单且具有高阻燃性能的阻燃多元醇组合物的制备方法。
本发明的另一目的在于提供该阻燃多元醇组合物的用途,该阻燃多元醇,用于制备阻燃聚氨酯硬质泡沫塑料。
本发明的实施方式之一是公开了一种阻燃多元醇组合物,所述阻燃多元醇组合物由含磷多元醇和聚醚多元醇组成,各多元醇的重量份数比如下:
其中,所述含磷多元醇为通过将含磷小分子与环氧基物质反应制备含磷阻燃多元醇,所述含磷阻燃多元醇的粘度为1500-3500 mpa·s,羟值在400-600mg KOH/g;
进一步地,所述含磷阻燃多元醇中含磷小分子的羟基与环氧基物质中环氧基的摩尔数比例为1:0.8至1:1。
作为本发明实施方式的进一步改进,所述含磷小分子包括磷酸酯单体,所述磷酸酯单体选自磷酸二甲酯、磷酸二乙酯、磷酸二丁酯、磷酸二苯酯、羟基磷酸酯、O,O’-二乙基-N,N-双(2-羟基乙基)氨甲基膦酸酯、三(一缩丙二醇)磷酸酯、三(一缩二丙二醇)亚磷酸酯、三(聚氧化烯烃)磷酸酯、三(聚氧化烯烃)亚磷酸酯、四羟甲基硫酸磷中至少一种。
作为本发明实施方式的进一步改进,所述环氧基物质,包括具有环氧基团的树脂或者具有环氧基团的稀释剂;
所述具有环氧基团的树脂为由环氧氯丙烷或甲基环氧氯丙烷和双酚A、双酚F或双酚砜反应得到的环氧树脂;
所述稀释剂为双酚A的环氧烷烃经加成的聚缩水甘油醚,或多元醇的聚缩水甘油醚,或多羧酸的聚缩水甘油酯及聚缩水甘油胺;
其中,所述多元醇包括聚丙二醇、1,6-己二醇、三羟甲基丙烷或甘油;
所述多羧酸包括己二酸、苯二甲酸或二聚物酸。
作为本发明实施方式的进一步改进,所述环氧基物质包括双酚A或双酚F与环氧氯丙烷制备的环氧树脂与活性稀释剂的混合物;
所述活性稀释剂为单活性稀释剂或双活性稀释剂;
所述单活性稀释剂为丁基缩水甘油醚、苯基缩水甘油醚或C12-C13缩水甘油醚;
所述双活性稀释剂为分子量为200-400的聚乙二醇缩水甘油醚或分子量为200-400的聚丙二醇缩水甘油醚。
作为本实施方式的进一步改进,所述的氧化烯烃包括环氧乙烷、环氧丙烷、环氧丁烷中至少一种。
作为本实施方式的进一步改进,所选的发泡剂选自常用的发泡剂,如环戊烷、异戊烷、五氟丙烯(245fa)、1-氯-3,3,3-三氟丙烯(LBA)、六氟丁烯(FEA-1100)中至少一种。
作为本实施方式的进一步改进,所述的异氰酸酯为多亚甲基多苯基异氰酸酯,所述异氰酸酯含量为30.5-32.0%,其粘度为150-250mPa·s.
作为本发明实施方式的进一步改进,所述聚醚多元醇I为含氮多元醇,由含氮起始剂与氧化烯烃通过加成反应制备;
其中,所述含氮起始剂选自三聚氰胺、三羟甲基三聚氰胺、三(2-羟乙基)异氰脲酸酯中的一种;所述聚醚多元醇II的典型特征粘度为400-800mpa·s,羟值为250-500mg KOH/g。
作为本发明实施方式的进一步改进,所述聚醚多元醇II选自乙二醇、丙二醇、一缩二乙二醇、二缩三乙二醇、新戊二醇、己二醇中的至少一种作为起始剂与氧化烯烃通过加成反应制备;所述聚醚多元醇II的典型特征粘度为150-250mpa·s,羟值为160-300mg KOH/g,平均官能度为1-2。
作为本发明实施方式的进一步改进,所述聚醚多元醇III是以甘油、三羟甲基丙烷中的至少一种作为起始剂与氧化烯烃通过加成反应制备得到;所述聚醚多元醇III的典型特征粘度为400-800mpa·s,羟值为250-500mgKOH/g,平均官能度为2-3。
本发明的实施方式之二是公开了上述阻燃多元醇组合物的制备方法,所述方法包括以下步骤:
将环氧基物质加入到反应釜中,保持反应釜中反应温度70-80℃;
滴加含磷小分子,0.5-1小时后滴加完成,将反应釜温度升高到90℃,反应3-5小时;
降低反应釜温度,出料。
本发明的实施方式之三是公开了上述阻燃多元醇组合物或上述的制备方法得到的阻燃多元醇组合物在制备聚氨酯硬质泡沫塑料中的应用。
其中,上述聚氨酯硬质泡沫塑料各原料重量份数比如下:
上述聚氨酯硬质泡沫塑料的制备方法包括以下步骤:
S1、将阻燃多元醇组合物在20-25℃混合2-3h,制成预白料;
S2、将发泡剂与预白料在温度为20-25℃、混合压力为2-3bar的条件下混合2-3h,制成第一混合物;
S3、将第一混合物和异氰酸酯在20-25℃,120-140bar压力下混合,注入预热40-50℃模腔,进行发泡和熟化;
S4、将冷却好的泡沫体脱模,进行性能测试。
再一方面,本发明的另一实施方式是公开了上述的聚氨酯硬质泡沫塑料或上述方法制备的聚氨酯硬质泡沫塑料在家电内部保温材料中的用途,在具体实施中,本发明所公开的聚氨酯硬质泡沫塑料复合材料可用于冰箱、冷柜、太阳能、燃气热水器和消毒柜家电内部保温。
本发明具有以下有益效果:
1)与添加物理阻燃剂相比,本案中提供的含有阻燃元素的多元醇通过化学方法引入到多元醇结构中,避免物理阻燃剂带来的迁移问题,能够长久的保持聚氨酯硬质泡沫具有良好的阻燃性能;且不会使聚氨酯材料的力学性能降低;
2)本方法制备的聚氨酯硬质泡沫阻燃利用含磷的泡沫受热时,容易脱水生成强酸磷酸,同时放出水蒸气带走热量,并阻隔氧气与泡沫接触的阻燃机理,同时磷酸能够碳化泡沫,阻隔外部热量往内传播,起到很好的阻燃效果;
3)与不加阻燃剂聚氨酯泡沫相比,本发明实施例泡沫阻燃性能有明显的改善;通过上述阻燃多元醇组合物以及上述方法制备出的聚氨酯硬质泡沫,组合料粘度低保证了发泡料的流动性好,能够快速充满模具;且制备出的聚氨酯硬质泡沫导热系数较低、综合性能较好;
4)本发明实施例还进一步公开了具有叔胺结构的阻燃多元醇组合物,对聚氨酯的反应本身具有相应的催化性,利用磷-氮协同的作用具有更佳的阻燃效果,氧指数较低、同时制备的聚氨酯导热系数较低,综合性能较好;
5)本发明实施例中引入的三聚氰胺等受热很容易分解的含氮化合物,受热产生氨气,能够阻隔氧气与泡沫接触,同时氨气能够膨胀碳层,阻止热量和火焰向内的传递,从而提高聚氨酯的阻燃效果。
6)本发明实施例制备的聚氨酯硬质泡沫强度高,导热系数低;通过这种聚氨酯硬质泡沫制备的冰箱具有更好的强度,更好的保温性能。
具体实施方式
为使本申请的目的、技术方案和优点更加清楚,下面将结合本申请具体实施方式对本申请技术方案进行清楚、完整地描述。显然,所描述的实施方式仅是本申请一部分实施方式,而不是全部的实施方式。基于本申请中的实施方式,本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施方式,都属于本申请保护的范围。
下面详细描述本发明的实施方式,下面描述的实施方式是示例性的,仅用于解释本发明,而不能理解为对本发明的限制。
本发明的实施方式之一是公开了一种阻燃多元醇组合物,该阻燃多元醇组合物由含磷多元醇和聚醚多元醇组成,各多元醇的重量份数比如下:
其中,所述含磷多元醇为通过将含磷小分子与环氧基物质反应制备含磷阻燃多元醇,所述含磷阻燃多元醇的粘度为1500-3500mpa·s,羟值在400-600mg KOH/g;
进一步地,含磷阻燃多元醇中含磷小分子的羟基与环氧基物质中环氧基的摩尔数比例为1:0.8至1:1。
作为本发明实施方式的进一步改进,含磷小分子包括磷酸酯单体,磷酸酯单体选自磷酸二甲酯、磷酸二乙酯、磷酸二丁酯、磷酸二苯酯、羟基磷酸酯、O,O’-二乙基-N,N-双(2-羟基乙基)氨甲基膦酸酯、三(一缩丙二醇)磷酸酯、三(一缩二丙二醇)亚磷酸酯、三(聚氧化烯烃)磷酸酯、三(聚氧化烯烃)亚磷酸酯、四羟甲基硫酸磷中至少一种。
作为本发明实施方式的进一步改进,环氧基物质,包括具有环氧基团的树脂或者具有环氧基团的稀释剂;
其中,具有环氧基团的树脂为由环氧氯丙烷或甲基环氧氯丙烷和双酚A、双酚F或双酚砜反应得到的环氧树脂;
优选地,稀释剂为双酚A的环氧烷烃经加成的聚缩水甘油醚,或多元醇的聚缩水甘油醚,或多羧酸的聚缩水甘油酯及聚缩水甘油胺;
上述多元醇包括聚丙二醇、1,6-己二醇、三羟甲基丙烷或甘油;
上述多羧酸包括己二酸、苯二甲酸或二聚物酸。
作为本发明实施方式的进一步改进,环氧基物质还可以包括双酚A或双酚F与环氧氯丙烷制备的环氧树脂,如可商业化生产并购买的E51、E20、E54、E44,与活性稀释剂的混合物;
一般地,活性稀释剂为单活性稀释剂或双活性稀释剂;
优选地,单活性稀释剂为丁基缩水甘油醚、苯基缩水甘油醚或C12-C13缩水甘油醚;
可选地,双活性稀释剂为分子量为200-400的聚乙二醇缩水甘油醚或分子量为200-400的聚丙二醇缩水甘油醚。
作为本实施方式的进一步改进,参与加成反应的氧化烯烃选自环氧乙烷、环氧丙烷、环氧丁烷中至少一种。
作为本实施方式的进一步改进,发泡剂选自常用的发泡剂,如环戊烷、异戊烷、五氟丙烯(245fa)、1-氯-3,3,3-三氟丙烯(LBA)、六氟丁烯(FEA-1100)中至少一种。
作为本实施方式的进一步改进,异氰酸酯为多亚甲基多苯基异氰酸酯,所述异氰酸酯含量为30.5-32.0%,其粘度为150-250mPa·s.
作为本发明实施方式的进一步改进,聚醚多元醇I为含氮多元醇,由含氮起始剂与氧化烯烃通过加成反应制备;氮元素也是典型的阻燃元素,氮元素的引入可以利用氮磷协同阻燃将
其中,所述含氮起始剂选自三聚氰胺、三羟甲基三聚氰胺、三(2-羟乙基)异氰脲酸酯中的一种;所述聚醚多元醇II的典型特征粘度为400-800mpa·s,羟值为250-500mg KOH/g。
作为本发明实施方式的进一步改进,聚醚多元醇II选自乙二醇、丙二醇、一缩二乙二醇、二缩三乙二醇、新戊二醇、己二醇中的至少一种作为起始剂与氧化烯烃通过加成反应制备;所述聚醚多元醇II的典型特征粘度为150-250mpa·s,羟值为160-300mg KOH/g,平均官能度为1-2。
作为本发明实施方式的进一步改进,聚醚多元醇III是以甘油、三羟甲基丙烷中的至少一种作为起始剂与氧化烯烃通过加成反应制备得到;所述聚醚多元醇III的典型特征粘度为400-800mpa·s,羟值为250-500mg KOH/g,平均官能度为2-3。
本发明的实施方式之二是公开了上述阻燃多元醇组合物的制备方法,具体包括以下步骤:
将环氧基物质加入到反应釜中,保持反应釜中反应温度70-80℃;
滴加含磷小分子,0.5-1小时后滴加完成,将反应釜温度升高到90℃,反应3-5小时;
降低反应釜温度,出料。
本发明的实施方式之三是公开了上述阻燃多元醇组合物或上述的制备方法得到的阻燃多元醇组合物在制备聚氨酯硬质泡沫塑料中的应用。
其中,上述聚氨酯硬质泡沫塑料各原料重量份数比如下:
上述聚氨酯硬质泡沫塑料的制备方法包括以下步骤:
S1、将阻燃多元醇组合物在20-25℃混合2-3h,制成预白料;
S2、将发泡剂与预白料在温度为20-25℃、混合压力为2-3bar的条件下混合2-3h,制成第一混合物;
S3、将第一混合物和异氰酸酯在20-25℃,120-140bar压力下混合,注入预热40-50℃模腔,进行发泡和熟化;
S4、将冷却好的泡沫体脱模,进行性能测试。
再一方面,本发明的另一实施方式是公开了上述的聚氨酯硬质泡沫塑料或上述方法制备的聚氨酯硬质泡沫塑料在家电内部保温材料中的用途,在具体实施中,本发明所公开的聚氨酯硬质泡沫塑料复合材料可用于冰箱、冷柜、太阳能、燃气热水器和消毒柜家电内部保温。
具体地,在本实施例涉及的阻燃多元醇组合物及其制备的聚氨酯硬质泡沫塑料的原料及添加剂的份数比具体见下表,包括不同物料及配比组成的具体实施例和现有技术中作为对比例;
实施例1
本发明实施例选用的磷酸小分子为磷酸二乙酯、环氧基物质为环氧树脂E51、分子量为300的聚乙二醇缩水甘油醚;
所述的阻燃多元醇制备方法为:将380g环氧树脂E51以及300g聚乙二醇缩水甘油醚加入到反应釜中,然后升高反应温度到70℃,滴加600g磷酸二乙酯,1小时滴加完成后,升温到90℃,反应4小时,降温出料。
所制备的阻燃多元醇,粘度在1500-2000mpa.s,羟值550-600mgKOH/g。
实施例2
本发明实施例选用的磷酸小分子为磷酸二丁酯,环氧基物质为环氧树脂E51、分子量为200的聚乙二醇缩水甘油醚;
所述的阻燃多元醇制备方法为:将380g环氧树脂E51以及200g聚乙二醇缩水甘油醚加入到反应釜中,然后升高反应温度到70℃,滴加800g磷酸二乙酯,1小时滴加完成后,升温到90℃,反应4小时,降温出料。
所制备的阻燃多元醇,粘度在1300-1600mpa.s,羟值530-550mgKOH/g。
实施例3
本发明实施例选用的含磷小分子为O,O`-二乙基-N,N-双(2-羟基乙基)氨甲基膦酸酯、环氧基物质为环氧树脂E51、分子量为200的聚乙二醇缩水甘油醚;
所述的阻燃多元醇制备方法为:将380g环氧树脂E51以及200g聚乙二醇缩水甘油醚加入到反应釜中,然后升高反应温度到70℃,滴加1000gO,O`-二乙基-N,N-双(2-羟基乙基)氨甲基膦酸酯,1小时滴加完成后,升温到90℃,反应5小时,降温出料。
所制备的阻燃多元醇,粘度在2100-2400mpa.s,羟值460-490mgKOH/g。
实施例4
本发明实施例选用的含磷小分子选用的物质为磷酸二乙酯和O,O`-二乙基-N,N-双(2-羟基乙基)氨甲基膦酸酯的混合物、环氧基物质为环氧树脂E20、分子量为200的聚乙二醇缩水甘油醚;
所述的阻燃多元醇制备方法为:将380g环氧树脂E51以及200g聚乙二醇缩水甘油醚加入到反应釜中,然后升高反应温度到70℃,滴加500gO,O`-二乙基-N,N-双(2-羟基乙基)氨甲基膦酸酯和200g磷酸二乙酯的混合物,1小时滴加完成后,升温到90℃,反应5小时,降温出料。
所制备的阻燃多元醇,粘度在1800-2300mpa.s,羟值480-530mgKOH/g。
将实施例1-4制备得到的含磷多元醇和聚醚多元醇I、II、III共同混合得到阻燃多元醇组合物,分别加入到实施例5-12中制备聚氨酯硬质泡沫塑料,并与现有技术的对比例1和对比例2进行阻燃性能和机械性能的对比;具体如下表所示:
将上述实施例制备得到的聚氨酯硬质泡沫塑料进行压缩强度、平均密度、导热系数、低温稳定性、闭孔率及氧指数的性能测试;经实验结果表明,相对于现有技术,本发明实施例通过在加入含磷阻燃剂,具备了显著提高的氧指数,明显提升了阻燃性能。
具体地,本发明的有益效果是:
1)与添加物理阻燃剂相比,本案中提供的含有阻燃元素的多元醇通过化学方法引入到多元醇结构中,避免物理阻燃剂带来的迁移问题,能够长久的保持聚氨酯硬质泡沫具有良好的阻燃性能;且不会使聚氨酯材料的力学性能降低;
2)本方法制备的聚氨酯硬质泡沫阻燃利用含磷的泡沫受热时,容易脱水生成强酸磷酸,同时放出水蒸气带走热量,并阻隔氧气与泡沫接触的阻燃机理,同时磷酸能够碳化泡沫,阻隔外部热量往内传播,起到很好的阻燃效果;
3)与不加阻燃剂聚氨酯泡沫相比,本发明实施例泡沫阻燃性能有明显的改善;通过上述阻燃多元醇组合物以及上述方法制备出的聚氨酯硬质泡沫,组合料粘度低保证了发泡料的流动性好,能够快速充满模具;且制备出的聚氨酯硬质泡沫导热系数较低、综合性能较好;
4)本发明实施例还进一步公开了具有叔胺结构的阻燃多元醇组合物,对聚氨酯的反应本身具有相应的催化性,利用磷-氮协同的作用具有更佳的阻燃效果,氧指数较低、同时制备的聚氨酯导热系数较低,综合性能较好;
5)本发明实施例中引入的三聚氰胺等受热很容易分解的含氮化合物,受热产生氨气,能够阻隔氧气与泡沫接触,同时氨气能够膨胀碳层,阻止热量和火焰向内的传递,从而提高聚氨酯的阻燃效果。
6)本发明实施例制备的聚氨酯硬质泡沫强度高,导热系数低;通过这种聚氨酯硬质泡沫制备的冰箱具有更好的强度,更好的保温性能。
应当理解,虽然本说明书按照实施方式加以描述,但并非每个实施方式仅包含一个独立的技术方案,说明书的这种叙述方式仅仅是为清楚起见,本领域技术人员应当将说明书作为一个整体,各实施方式中的技术方案也可以经适当组合,形成本领域技术人员可以理解的其他实施方式。
上文所列出的一系列的详细说明仅仅是针对本发明的可行性实施方式的具体说明,并非用以限制本发明的保护范围,凡未脱离本发明技艺精神所作的等效实施方式或变更均应包含在本发明的保护范围之内。
Claims (5)
1.一种阻燃多元醇组合物,其特征在于,所述阻燃多元醇组合物由含磷多元醇和聚醚多元醇组成,各多元醇的重量份数比如下:
含磷多元醇: 20-40份
聚醚多元醇I: 20-40份
聚醚多元醇II:20-30份
聚醚多元醇III:20-30份;
所述含磷多元醇为通过将含磷小分子与环氧基物质反应制备含磷阻燃多元醇,所述含磷阻燃多元醇的粘度为1500-3500 mpa∙s,羟值在400-600mgKOH/g;
所述含磷阻燃多元醇中含磷小分子的羟基与环氧基物质中环氧基的摩尔数比例为1:0.8至1:1;
其中,所述环氧基物质包括双酚A或双酚F与环氧氯丙烷制备的环氧树脂与活性稀释剂的混合物;所述活性稀释剂为单活性稀释剂或双活性稀释剂;所述单活性稀释剂为丁基缩水甘油醚、苯基缩水甘油醚或C12-C13缩水甘油醚;所述双活性稀释剂为分子量为200-400的聚乙二醇缩水甘油醚或分子量为200-400的聚丙二醇缩水甘油醚;
所述聚醚多元醇I为含氮多元醇,由含氮起始剂与氧化烯烃通过加成反应制备得到;其中,所述含氮起始剂选自三聚氰胺、三羟甲基三聚氰胺、三(2-羟乙基)异氰脲酸酯中的一种;所述聚醚多元醇I的典型特征粘度为400-800 mpa∙s,羟值为250-500mg KOH/g;
所述聚醚多元醇II选自由乙二醇、丙二醇、一缩二乙二醇、二缩三乙二醇、新戊二醇、己二醇中的至少一种作为起始剂与氧化烯烃通过加成反应制备得到;所述聚醚多元醇II的典型特征粘度为150-250 mpa∙s,羟值为160-300mg KOH/g,平均官能度为1-2;
所述聚醚多元醇III是以甘油、三羟甲基丙烷中的至少一种作为起始剂与氧化烯烃通过加成反应制备得到;所述聚醚多元醇III的典型特征粘度为400-800 mpa∙s,羟值为250-500mg KOH/g,平均官能度为2-3。
2.根据权利要求1所述的阻燃多元醇组合物,其特征在于,所述含磷小分子包括磷酸酯单体,所述磷酸酯单体选自磷酸二甲酯、磷酸二乙酯、磷酸二丁酯、磷酸二苯酯、O,O’-二乙基-N,N-双(2-羟基乙基)氨甲基膦酸酯、三(一缩二丙二醇)亚磷酸酯、三(聚氧化烯烃)磷酸酯、三(聚氧化烯烃)亚磷酸酯、四羟甲基硫酸磷中至少一种。
3.根据权利要求1所述的阻燃多元醇组合物,其特征在于,所述含磷多元醇通过包括以下步骤的方法制备得到:
将环氧基物质加入到反应釜中,保持反应釜中反应温度70-80℃;
滴加含磷小分子,0.5-1小时后滴加完成,将反应釜温度升高到90℃,反应3-5小时;
降低反应釜温度,出料。
4.一种根据权利要求1-3任一项所述的阻燃多元醇组合物在制备聚氨酯硬质泡沫塑料中的应用。
5.一种根据权利要求4中所述的聚氨酯硬质泡沫塑料,其特征在于,所述聚氨酯硬质泡沫塑料的原料重量份数比如下:
根据权利要求1-3任一项所述的阻燃多元醇组合物: 100份
表面活性剂: 1-2份
发泡剂: 10-30份
异氰酸酯: 140份。
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