CN107722350B - A kind of polyhydroxy silicon nitrogen type flame retardant and its preparation method and the application in anti-inflaming polyurethane hard foam material - Google Patents
A kind of polyhydroxy silicon nitrogen type flame retardant and its preparation method and the application in anti-inflaming polyurethane hard foam material Download PDFInfo
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- CN107722350B CN107722350B CN201710973981.1A CN201710973981A CN107722350B CN 107722350 B CN107722350 B CN 107722350B CN 201710973981 A CN201710973981 A CN 201710973981A CN 107722350 B CN107722350 B CN 107722350B
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- flame retardant
- oxide
- type flame
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 74
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000004814 polyurethane Substances 0.000 title claims abstract description 43
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 43
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical compound [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000006261 foam material Substances 0.000 title claims description 26
- 238000002360 preparation method Methods 0.000 title claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 41
- 150000003077 polyols Chemical class 0.000 claims abstract description 36
- 229920005862 polyol Polymers 0.000 claims abstract description 29
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000006260 foam Substances 0.000 claims abstract description 19
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 17
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 15
- 229920000570 polyether Polymers 0.000 claims abstract description 15
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 15
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 13
- 239000012153 distilled water Substances 0.000 claims abstract description 11
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 5
- 238000005187 foaming Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 132
- 239000000243 solution Substances 0.000 claims description 81
- 235000019441 ethanol Nutrition 0.000 claims description 54
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 36
- 239000007822 coupling agent Substances 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 30
- -1 dimethylamino-propyl Chemical group 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 22
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 22
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 12
- 235000005074 zinc chloride Nutrition 0.000 claims description 11
- 239000011592 zinc chloride Substances 0.000 claims description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 10
- 239000011541 reaction mixture Substances 0.000 claims description 10
- 239000012265 solid product Substances 0.000 claims description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 9
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 9
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 7
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical group [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002210 silicon-based material Substances 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 125000003118 aryl group Chemical group 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000002347 injection Methods 0.000 claims description 3
- 239000007924 injection Substances 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims 2
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical compound C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 claims 1
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 229940031098 ethanolamine Drugs 0.000 claims 1
- 150000003377 silicon compounds Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 28
- 239000011347 resin Substances 0.000 description 16
- 229920005989 resin Polymers 0.000 description 16
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 10
- 239000004615 ingredient Substances 0.000 description 9
- 230000007613 environmental effect Effects 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 150000004754 hydrosilicons Chemical class 0.000 description 8
- ADIMAYPTOBDMTL-UHFFFAOYSA-N oxazepam Chemical compound C12=CC(Cl)=CC=C2NC(=O)C(O)N=C1C1=CC=CC=C1 ADIMAYPTOBDMTL-UHFFFAOYSA-N 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 7
- 229910000077 silane Inorganic materials 0.000 description 7
- 229920005830 Polyurethane Foam Polymers 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000004088 foaming agent Substances 0.000 description 6
- 239000011496 polyurethane foam Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical group C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 4
- DPXFJZGPVUNVOT-UHFFFAOYSA-N 3-[1,3-bis[3-(dimethylamino)propyl]triazinan-5-yl]-n,n-dimethylpropan-1-amine Chemical class CN(C)CCCC1CN(CCCN(C)C)NN(CCCN(C)C)C1 DPXFJZGPVUNVOT-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 229940043237 diethanolamine Drugs 0.000 description 2
- 230000009931 harmful effect Effects 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 1
- JQYOCVPEXWBLGO-UHFFFAOYSA-N [N].[Si].[P] Chemical compound [N].[Si].[P] JQYOCVPEXWBLGO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920003232 aliphatic polyester Polymers 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- MSSNHSVIGIHOJA-UHFFFAOYSA-N pentafluoropropane Chemical compound FC(F)CC(F)(F)F MSSNHSVIGIHOJA-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/544—Silicon-containing compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1876—Preparation; Treatments not provided for in C07F7/20 by reactions involving the formation of Si-C linkages
-
- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4018—Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
- C08G18/6611—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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Abstract
The invention discloses a kind of polyhydroxy phenyl ring silicon nitrogen type flame retardants, it is characterized in that it has following chemical structure:Wherein R1For following structural formula or its analog:Wherein R2For one kind or its analog of following structural formula:With polyhydroxy phenyl ring silicon nitrogen type flame retardant of the invention, using polyether polyol, polyester polyol, polyisocyanates, catalyst, stabilizer, crosslinking agent, modified nano oxide compound, fire retardant, distilled water as primary raw material, through mixing, high-speed stirred, foaming, curing, full water foamed flame retarded rigid polyurethane material is obtained.The full water foamed flame retardant polyurethane rigid foam of gained mechanical property with higher and flame retardant property, 58.5~64.5kg/m of density3, 0.405~0.45MPa of compressive strength, drawing 0.53~0.68MPa of Zhong Qiangdu, limit oxygen index 28.5~34.5%.
Description
Technical field
The present invention relates to a kind of silicon nitrogenated flame retardant and full water foamed hard polyurethane foams.
Background technique
Rigid polyurethane material is one of current most popular high molecular material, has low-density, and high specific strength is excellent
Different wear-resisting property, low thermal conductivity and excellent damping sound absorption qualities etc..The shortcomings that hard polyurethane foam is inflammable and resistance to height
Warm nature can be poor, and contact fire source can generate flame immediately, and the life and property to the mankind bring huge threat, are applied to
Produce great limitation.Reactive flame retardant participates in polymerization reaction in polyurethane synthesis process and is integrated to ignition-proof element
On material molecule main chain or side chain, to make the polyurethane material prepared that there is flame retardant property, this based flame retardant and matrix material
Expect that compatibility is good, flame retarding efficiency is high.Phosphorus system, silicon-series five-retardant have flame retarding efficiency high, flame retardant effect lasting stability and at low cost
Etc. advantages, and the compound of aromatic structure or heterocycle structure has the function of reinforcing material molecule chain rigidity to a certain extent.
Chinese publication CN101906248A discloses a kind of high compression-strength rigid-enhancement type hard polyurethane foaming plastic, with virtue
Fragrant compounds of groupFor the rigid structure component of reinforced polyurethane foam compressive strength,
This aromatic compound enhances the mechanical property of material, does not have greatly improved to the flame retardant property of material but.
The preparation of hard polyurethane foam generally uses low boiling point fluorochlorohydrocarbon class compound as foaming agent, as CFC-F11,
HFC-141b, HFC-245fa, these fluorinated foaming agents have certain destruction to ozone, and using pentane as representative
Hydrocarbon blowing agents, it is toxic, inflammable and explosive, and to the harmful effect of environment.The foam process using water as foaming agent is opened in recent years
Beginning is widely studied, and water and isocyanates reaction generate CO2As foaming agent, ozone damped expoential (ODP) is 0, and
Foam process is more simple and safe.However compared with physical blowing system, that there is intensity is low for the full water foamed material prepared,
The disadvantages of poor, foams embrittlement of dimensional stability etc..Some specific nano-oxides are by being modified, reunion in the material
Phenomenon disappears, and has good compatibility with material, also improves the drawing Zhong Qiangdu of material, wearability and anti-aging to a certain extent
Performance, so that foams are not easy embrittlement.
The ignition-proof elements such as silicon, nitrogen are introduced into the molecular structure of polyurethane material by the present invention, in combination with rigid heat resistant
Benzene ring structure enhances the flame retardant property and molecule chain rigidity cohesive force of rigid polyurethane material.Silicon, nitrogen compound it is fire-retardant
Process acts on the condensed phase and gas phase of material combustion simultaneously respectively, has certain two-phase cooperative flame retardant effect.Abandon physics
The use of foaming agent fluorochlorohydrocarbon class compound, prepares hard polyurethane foam using full water foamed system, will further be modified
Nano-oxide is added thereto, largely overcome the low full water foamed rigid poly urethanes strength of materials, poor dimensional stability,
The disadvantages of foams embrittlement.
Summary of the invention
In order to solve the above problems existing in the present technology, the present invention provides a kind of full water foamed anti-inflaming polyurethane hard foams
Material and preparation method thereof.The method that one aspect of the present invention utilizes chemical structure MOLECULE DESIGN, prepares polyhydroxy phenyl ring silicon nitrogen
Flame retardant, the presence of silicon N structure and benzene radicals enhance the flame retardant property and heat resistance of material, on the other hand, use
The water that ODP value is zero introduces modified nano oxide compound as foaming agent, effectively improves the drawing Zhong Qiangdu of material foams body, wear-resisting
Property and anti-aging property, and foams is made to be not easy embrittlement.In order to realize the above goal of the invention, the technical solution adopted by the present invention
It is as follows:
A kind of polyhydroxy phenyl ring silicon nitrogen type flame retardant, it has following chemical structure:
Wherein R1For one kind of following structural formula:
R2For one kind of following structural formula:
A method of above-mentioned polyhydroxy phenyl ring silicon nitrogen type flame retardant being prepared, it is reacted as follows:
It includes the following steps:
Step 1 under the conditions of being stirred at room temperature, parahydroxyben-zaldehyde is dissolved in ethyl alcohol and forms solution A, and double aminobenzene cyclisation are closed
Object, which is dissolved in ethyl alcohol, forms B solution, and B solution is added dropwise in solution A at 25-30 DEG C, and time for adding control is in 1-2h, drop
It is warming up to 40-55 DEG C after adding, reacts 2-4h, obtains a kind of polyol containing carbon-to-nitrogen double bon, double ammonia
Base benzene ring compound is one of following 8 kinds of compounds:
Under step 2, nitrogen protection, silicon-containing compound is added in the reaction system in above-mentioned steps 1, while being added and urging
Reaction mixture is warming up to 70-85 DEG C, reacts 8-16h, be poured into petroleum ether and stir after being cooled to room temperature by agent zinc chloride
0.5-1.5h is mixed, filters out solid product, then obtain polyhydroxy benzenes in 50-75 DEG C of vacuum drying 12-24h with cold ethanol washing
Ring silicon nitrogen type flame retardant, the silicon-containing compound are one of following two kinds of compounds:
The above-mentioned method for preparing polyhydroxy phenyl ring Phosphorus-nitrogen flame retardant, parahydroxyben-zaldehyde and second in the solution A
The mass ratio of alcohol is 1:8-15, and the mass ratio of double amino benzene ring compounds and ethyl alcohol is 1:5-10 in B solution, double aminobenzene cyclisation
The molar ratio for closing object and parahydroxyben-zaldehyde is 1: 2-2.5, and the molar ratio of double amino benzene ring compounds and silicon-containing compound is 1:
The mass ratio of 3-3.5, parahydroxyben-zaldehyde and petroleum ether is 1: 35-50, and the mass ratio of parahydroxyben-zaldehyde and zinc chloride is 1:
0.02-0.05。
Above-mentioned polyhydroxy phenyl ring silicon nitrogen type flame retardant is preparing the application in full water foamed anti-inflaming polyurethane hard foam material.
Above-mentioned full water foamed anti-inflaming polyurethane hard foam material, it includes two kinds of components of A, B, by mass, in component A
Component number are as follows: polyether polyol: 30-85 parts, polyester polyol: 15-30 parts, stabilizer: 2-4 parts, catalyst: 0.5-3 parts,
Crosslinking agent: 0.5-1.5 parts, distilled water: 3-10 parts, modified nano oxide compound: 2-10 parts, above-mentioned polyhydroxy benzenes silicon phosphorus-nitrogen type resistance
Combustion agent: 5-12 parts;Component number in B component are as follows: polyisocyanates: 60-150 parts.
Above-mentioned full water foamed anti-inflaming polyurethane hard foam material, stabilizer is organosilicon foam stabilizer AK- in the component A
8805, one or more of combinations of AK-8811, AK-8803, AK-8832;Catalyst is triethylene diamine, N, N- dimethyl
Cyclohexylamine, N, N- dimethyl benzylamine, ethylenediamine, cyclohexylamine, 1,3,5- tri- (dimethylamino-propyl) Hexahydrotriazines, pentamethyl diethyl
One or more of combinations of alkene triamine;Crosslinking agent be trimethylolpropane, triethanolamine, diethanol amine, glycerol one kind or
Several combinations;The polyether polyol is the one or more of polytetrahydrofuran polyol or polyoxypropylene polyol, hydroxyl
Value is 420-480mgKOH/g, and viscosity is 2000-6000mPa.s (25 DEG C);Polyester polyol be aliphatic polyester polyols or
The one or more of aromatic polyester polyol, their hydroxyl value are 100-400mgKOH/g, viscosity 2000-3000mPa.s
(25℃);The polyisocyanates is poly methylene poly phenyl poly isocyanate (PAPI).
Above-mentioned full water foamed anti-inflaming polyurethane hard foam material, modified nano oxide compound is nano-oxide in the component A
Through obtained by coupling agent modified processing, wherein nano-oxide is nano-titanium dioxide (TiO2), nano silica (SiO2), receive
Rice zinc oxide (ZnO), nano aluminium oxide (Al2O3), nanometer antimony pentoxide (Sb2O5), nano zircite (ZrO2), it is nano oxidized
Cerium (CeO2), nano iron oxide (Fe2O3), one or more of combinations of nano ceramics, coupling agent is Silane coupling agent KH550
Or one kind of titanate coupling agent 201, the mass ratio of coupling agent and nano-oxide are 1: 15-20, first configuration contains coupling agent
Nano-oxide is placed in the ethanol solution containing coupling agent by the ethanol solution of 2%-4%, is filtered after stirring 0.5-1h, filter cake
Dry 2h, is made modified nano oxide compound at 80-95 DEG C.
A kind of preparation method of above-mentioned full water foamed anti-inflaming polyurethane hard foam material, it is that polyether polyols in component A are pure and mild
Polyester polyol mix high-speed stirred it is uniform, other auxiliary agents are added after mixing evenly, with B component by high-pressure foam machine equipment into
Row is sufficiently mixed, by foaming machine gun head injection constant temperature sealed mold, a series of processes such as foamed, curing, demoulding are hindered
Flame-retardant polyurethane rigid foam material.
The present invention prepares a kind of based on full water foamed fire-retardant poly- on the basis of synthesizing a kind of silicon N structure fire retardant
Urethane rigid foam.The ignition-proof elements such as silicon, nitrogen are introduced into the molecular structure of polyurethane material, in combination with rigid heat resistant benzene
Ring structure enhances the flame retardant property and molecule chain rigidity of rigid polyurethane material.Abandon physical blowing agent fluorochlorohydrocarbon class chemical combination
The use of object prepares hard polyurethane foam using full water foamed system, is further added thereto modified nano oxide compound,
The disadvantages of largely overcoming the low full water foamed rigid poly urethanes strength of materials, poor dimensional stability, foams embrittlement.This
Advantageous effect of the invention is as follows:
1. the present invention prepares flame retardant polyurethane rigid foam, equal harmful elements are halogen-free, are avoided in combustion
Toxic gas and a large amount of smog are generated, and contains the good benzene ring structure of thermal stability and fire-retardant silicon nitrogen knot in molecular chain structure
Structure enhances the thermal stability and flame retardant property of hard polyaminoester;
2. the present invention is to be introduced modified nano oxide compound wherein based on full water foamed flame retardant polyurethane rigid foam,
The disadvantages of avoiding the low full water foamed rigid poly urethanes strength of materials, poor dimensional stability, foams embrittlement.Gained is full water foamed
Flame retardant polyurethane rigid foam mechanical property with higher and flame retardant property, 58.5~64.5kg/m of density3, compressive strength
0.405~0.45MPa draws 0.53~0.68MPa of Zhong Qiangdu, limit oxygen index 285~345%.
Specific embodiment
It is full water foamed that polyhydroxy phenyl ring silicon nitrogen type flame retardant and one kind of the invention are illustrated using embodiment below
Anti-inflaming polyurethane hard foam material and preparation method thereof.Embodiment is that the present invention is described in further detail, but they are not right
The present invention, which is constituted, to be limited.
A kind of full water foamed anti-inflaming polyurethane hard foam material of the invention is prepared by the following method:
Polyalcohol and various auxiliary agents in component A are weighed by recipe ingredient, after being mixed evenly, passes through high pressure with B component
Foaming machine equipment is sufficiently mixed, in the foamed machine gun head injection constant temperature sealed mold of the A, B component after being sufficiently mixed, through sending out
A series of processes such as bubble, curing, demoulding obtain anti-inflaming polyurethane hard foam material.
Embodiment 1:
The preparation of fire retardant:
1. under the conditions of being stirred at room temperature, 5.0g (0.041mol) parahydroxyben-zaldehyde is dissolved in shape in 75g (95ml) ethanol solution
At solution A, 4,4 '-benzidine of 3.0g (0.0164mol), which is dissolved in 30g (38ml) ethanol solution, forms B solution, at 30 DEG C
B solution is added dropwise in solution A, time for adding control is warming up to 55 DEG C after 2h, completion of dropwise addition, reacts 4h, obtains one
Polyol of the kind containing carbon-to-nitrogen double bon;
2. under nitrogen protection, hydrosilicon trimethoxy hydrogen silane is added in the hybrid system in above-mentioned 1, simultaneously
Catalyst zinc chloride 0.25g is added, reaction mixture is warming up to 85 DEG C, 16h is reacted, is poured into 250g after being cooled to room temperature
1.5h is stirred in the petroleum ether of (386ml), solid product is obtained by filtration, then washed 5 times with cold alcohol solution, it is dry in 75 DEG C of vacuum
It is dry for 24 hours, obtain polyhydroxy phenyl ring silicon nitrogen type flame retardant.
Polyol structure containing carbon-to-nitrogen double bon are as follows:
Polyhydroxy phenyl ring silicon nitrogen type flame retardant compound structure are as follows:
The preparation of modified nano oxide compound:
The mass ratio of Silane coupling agent KH550 and nano aluminium oxide is 1: 20, configures the ethanol solution containing coupling agent 4%,
Nano aluminium oxide is placed in the ethanol solution containing coupling agent, is filtered after stirring 1h, filter cake dry 2h at 95 DEG C is made and is modified
Nano aluminium oxide.
The recipe ingredient for preparing full water foamed anti-inflaming polyurethane hard foam material is as follows:
Polyether polyol (hydroxyl value 470mgKOH/g, viscosity 3000mPa.s, HK4110, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides): 85 parts
Polyester polyol (hydroxyl value 204mgKOH/g, viscosity 2000mPa.s, HK2054, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides): 30 parts
AK-8803 (Jiangsu Maysta Chemical Co., Ltd.'s offer): 4 parts
1,3,5- tri- (dimethylamino-propyl) Hexahydrotriazine (Yutai County Hai Na Environmental Protection Technology Co., Ltd): 3 parts
Trimethylolpropane (Shandong Lecron New Energy Saving Materials Co., Ltd.'s offer): 1.5 parts
Polyhydroxy phenyl ring silicon nitrogen type flame retardant (is made by oneself) according to the above method: 12 parts
Modified nano-alumina (offer of Nanjing Tian Hang new material Co., Ltd): 10 parts
Distilled water: 10 parts
Poly methylene poly phenyl poly isocyanate (offer of Henan Longhua chemical product Co., Ltd, Zhengzhou section): 150 parts
Embodiment 2:
The preparation of fire retardant:
1. under the conditions of being stirred at room temperature, it is molten that 5.0g (0.041mol) parahydroxyben-zaldehyde is dissolved in formation A in 40g ethanol solution
Liquid, 0.0205mol3,3 '-dimethoxy, 4,4 '-benzidine, which is dissolved in 25g ethanol solution, forms B solution, by B at 25 DEG C
Solution is added dropwise in solution A, and time for adding control is warming up to 40 DEG C after 1h, completion of dropwise addition, is reacted 2h, is obtained one kind and contain
There is the polyol of carbon-to-nitrogen double bon;
2. under nitrogen protection, hydrosilicon trimethoxy hydrogen silane is added in the hybrid system in above-mentioned 1, simultaneously
Catalyst zinc chloride 0.1g is added, reaction mixture is warming up to 70 DEG C, 8h is reacted, is poured into 175g's after being cooled to room temperature
0.5h is stirred in petroleum ether, solid product is obtained by filtration, then washed 5 times with cold alcohol solution, in 50 DEG C of vacuum drying 12h, is obtained
To polyhydroxy phenyl ring silicon nitrogen type flame retardant.
Polyol structure containing carbon-to-nitrogen double bon are as follows:
Polyhydroxy phenyl ring silicon nitrogen type flame retardant compound structure are as follows:
The preparation of modified nano oxide compound:
The mass ratio of titanate coupling agent 201 and nano-titanium dioxide is 1: 15, and ethyl alcohol of the configuration containing coupling agent 2% is molten
Nano-titanium dioxide is placed in the ethanol solution containing coupling agent by liquid, is filtered after stirring 0.5h, filter cake dry 2h at 80 DEG C,
Modified nano-titanium dioxide is made.
The recipe ingredient for preparing full water foamed anti-inflaming polyurethane hard foam material is as follows:
Polyether polyol (hydroxyl value 480mgKOH/g, viscosity 6000mPa.s, HK8205, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides): 30 parts
Polyester polyol (hydroxyl value 400mgKOH/g, viscosity 2000mPa.s, HK3022, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides): 15 parts
AK-8805 (Jiangsu Maysta Chemical Co., Ltd.'s offer): 2 parts
Triethylene diamine (Yutai County Hai Na Environmental Protection Technology Co., Ltd): 0.5 part
Triethanolamine (Shandong Lecron New Energy Saving Materials Co., Ltd.'s offer): 0.5 part
Polyhydroxy phenyl ring silicon nitrogen type flame retardant (is made by oneself) according to the above method: 5 parts
Modified nano-titanium dioxide (offer of Nanjing Tian Hang new material Co., Ltd): 2 parts
Distilled water: 3 parts
Poly methylene poly phenyl poly isocyanate (offer of Henan Longhua chemical product Co., Ltd, Zhengzhou section): 60 parts
Embodiment 3:
The preparation of fire retardant:
1. under the conditions of being stirred at room temperature, 5.0g (0.041mol) parahydroxyben-zaldehyde is dissolved in shape in 75g (95ml) ethanol solution
At solution A, 0.0164mol3,3 '-diaminobenzene sulfones, which are dissolved in 30g (38ml) ethanol solution, forms B solution, at 30 DEG C that B is molten
Liquid is added dropwise in solution A, and time for adding control is warming up to 55 DEG C after 1h, completion of dropwise addition, is reacted 3h, is obtained one kind and contain
The polyol of carbon-to-nitrogen double bon;
2. under nitrogen protection, hydrosilicon trimethoxy hydrogen silane is added in the hybrid system in above-mentioned 1, simultaneously
Catalyst zinc chloride 0.25g is added, reaction mixture is warming up to 85 DEG C, 10h is reacted, is poured into 250g after being cooled to room temperature
1.5h is stirred in the petroleum ether of (386ml), solid product is obtained by filtration, then washed 5 times with cold alcohol solution, it is dry in 75 DEG C of vacuum
It is dry for 24 hours, obtain polyhydroxy phenyl ring silicon nitrogen type flame retardant.
Polyol structure containing carbon-to-nitrogen double bon are as follows:
Polyhydroxy phenyl ring silicon nitrogen type flame retardant compound structure are as follows:
The preparation of modified nano oxide compound:
The mass ratio of Silane coupling agent KH550 and nano zine oxide is 1: 20, configures the ethanol solution containing coupling agent 4%,
Nano aluminium oxide is placed in the ethanol solution containing coupling agent, is filtered after stirring 1h, filter cake dry 2h at 95 DEG C is made and is modified
Nano zine oxide.
The recipe ingredient for preparing full water foamed anti-inflaming polyurethane hard foam material is as follows:
(hydroxyl value 420mgKOH/g, viscosity 2000mPa.s, HK4110G, Jining of Shandong Province Hua Kai resin are limited for polyether polyol
Company provides): 55 parts
Polyester polyol (hydroxyl value 100mgKOH/g, viscosity 3000mPa.s, HK2100, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides): 30 parts
AK-8811 (Jiangsu Maysta Chemical Co., Ltd.'s offer): 2 parts
Ethylenediamine (Yutai County Hai Na Environmental Protection Technology Co., Ltd): 3 parts
Diethanol amine (Shandong Lecron New Energy Saving Materials Co., Ltd.'s offer): 1.0 parts
Polyhydroxy phenyl ring silicon nitrogen type flame retardant (is made by oneself) according to the above method: 12 parts
Modified nano zinc oxide (offer of Nanjing Tian Hang new material Co., Ltd): 10 parts
Distilled water: 10 parts
Poly methylene poly phenyl poly isocyanate (offer of Henan Longhua chemical product Co., Ltd, Zhengzhou section): 100 parts
Embodiment 4:
The preparation of fire retardant:
1. under the conditions of being stirred at room temperature, 5.0g (0.041mol) parahydroxyben-zaldehyde is dissolved in shape in 75g (95ml) ethanol solution
At solution A, 0.0164mol4,4 '-diaminobenzene sulfones, which are dissolved in 30g (38ml) ethanol solution, forms B solution, at 30 DEG C that B is molten
Liquid is added dropwise in solution A, and time for adding control is warming up to 55 DEG C after 1h, completion of dropwise addition, is reacted 2h, is obtained one kind and contain
The polyol of carbon-to-nitrogen double bon;
2. under nitrogen protection, hydrosilicon trimethoxy hydrogen silane is added in the hybrid system in above-mentioned 1, simultaneously
Catalyst zinc chloride 0.25g is added, reaction mixture is warming up to 80 DEG C, 16h is reacted, is poured into 250g after being cooled to room temperature
1.5h is stirred in the petroleum ether of (386ml), solid product is obtained by filtration, then washed 5 times with cold alcohol solution, it is dry in 75 DEG C of vacuum
Dry 20h obtains polyhydroxy phenyl ring silicon nitrogen type flame retardant.
Polyol structure containing carbon-to-nitrogen double bon are as follows:
Polyhydroxy phenyl ring silicon nitrogen type flame retardant compound structure are as follows:
The preparation of modified nano oxide compound:
Silane coupling agent KH550 and the mass ratio of nano silica are 1: 15, and ethyl alcohol of the configuration containing coupling agent 3% is molten
Nano aluminium oxide is placed in the ethanol solution containing coupling agent by liquid, is filtered after stirring 1h, and filter cake dry 2h at 95 DEG C is made
Modified manometer silicon dioxide.
The recipe ingredient for preparing full water foamed anti-inflaming polyurethane hard foam material is as follows:
Polyether polyol (hydroxyl value 430mgKOH/g, viscosity 3000mPa.s, HK8210, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides): 65 parts
Polyester polyol (hydroxyl value 280mgKOH/g, viscosity 2000mPa.s, HK2043, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides): 30 parts
AK-8832 (Jiangsu Maysta Chemical Co., Ltd.'s offer): 4 parts
N, N- dimethyl benzylamine (Yutai County Hai Na Environmental Protection Technology Co., Ltd): 3 parts
Glycerol (Shandong Lecron New Energy Saving Materials Co., Ltd.'s offer): 1.5 parts
Polyhydroxy phenyl ring silicon nitrogen type flame retardant (is made by oneself) according to the above method: 12 parts
Modified manometer silicon dioxide (offer of Nanjing Tian Hang new material Co., Ltd): 10 parts
Distilled water: 10 parts
Poly methylene poly phenyl poly isocyanate (offer of Henan Longhua chemical product Co., Ltd, Zhengzhou section): 100 parts
Embodiment 5:
The preparation of fire retardant:
1. under the conditions of being stirred at room temperature, 5.0g (0.041mol) parahydroxyben-zaldehyde is dissolved in shape in 75g (95ml) ethanol solution
At solution A, 0.0164mol4,4 '-are dissolved in 30g (38ml) ethanol solution diamino-benzene and form B solution, by B solution at 30 DEG C
It is added dropwise in solution A, time for adding control is warming up to 55 DEG C after 2h, completion of dropwise addition, reacts 4h, obtains one kind and contain carbon
The polyol of nitrogen double bond;
2. under nitrogen protection, hydrosilicon trimethoxy hydrogen silane is added in the hybrid system in above-mentioned 1, simultaneously
Catalyst zinc chloride 0.25g is added, reaction mixture is warming up to 85 DEG C, 16h is reacted, is poured into 250g after being cooled to room temperature
1.5h is stirred in the petroleum ether of (386ml), solid product is obtained by filtration, then washed 5 times with cold alcohol solution, it is dry in 75 DEG C of vacuum
It is dry for 24 hours, obtain polyhydroxy phenyl ring silicon nitrogen type flame retardant.
Polyol structure containing carbon-to-nitrogen double bon are as follows:
Polyhydroxy phenyl ring silicon nitrogen type flame retardant compound structure are as follows:
The preparation of modified nano oxide compound:
The mass ratio of titanate coupling agent 201 and nanometer antimony pentoxide is 1:20, and ethyl alcohol of the configuration containing coupling agent 4% is molten
Nano aluminium oxide is placed in the ethanol solution containing coupling agent by liquid, is filtered after stirring 1h, and filter cake dry 2h at 95 DEG C is made
Modified Nano antimony pentoxide.
The recipe ingredient for preparing full water foamed anti-inflaming polyurethane hard foam material is as follows:
Polyether polyol (hydroxyl value 470mgKOH/g, viscosity 3000mPa.s, HK4110, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides): 75 parts
Polyester polyol (hydroxyl value 204mgKOH/g, viscosity 2000mPa.s, HK2054, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides): 30 parts
AK-8803 (Jiangsu Maysta Chemical Co., Ltd.'s offer): 4 parts
Cyclohexylamine (Yutai County Hai Na Environmental Protection Technology Co., Ltd): 3 parts
Trimethylolpropane (Shandong Lecron New Energy Saving Materials Co., Ltd.'s offer): 1.5 parts
Polyhydroxy phenyl ring silicon nitrogen type flame retardant (is made by oneself) according to the above method: 10 parts
Modified Nano antimony pentoxide (offer of Nanjing Tian Hang new material Co., Ltd): 10 parts
Distilled water: 10 parts
Poly methylene poly phenyl poly isocyanate (offer of Henan Longhua chemical product Co., Ltd, Zhengzhou section): 120 parts
Embodiment 6:
The preparation of fire retardant:
1. under the conditions of being stirred at room temperature, 5.0g (0.041mol) parahydroxyben-zaldehyde is dissolved in shape in 75g (95ml) ethanol solution
At solution A, 0.0164mol3,3 ' dimethyl, 4,4 '-two phenylamino, which is dissolved in 30g (38ml) ethanol solution, forms B solution, at 30 DEG C
B solution is added dropwise in solution A, time for adding control is warming up to 50 DEG C after 2h, completion of dropwise addition, reacts 4h, obtains one
Polyol of the kind containing carbon-to-nitrogen double bon;
2. under nitrogen protection, hydrosilicon trimethoxy hydrogen silane is added in the hybrid system in above-mentioned 1, simultaneously
Catalyst zinc chloride 0.25g is added, reaction mixture is warming up to 85 DEG C, 10h is reacted, is poured into 250g after being cooled to room temperature
1.5h is stirred in the petroleum ether of (386m1), solid product is obtained by filtration, then washed 5 times with cold alcohol solution, it is dry in 75 DEG C of vacuum
It is dry for 24 hours, obtain polyhydroxy phenyl ring silicon nitrogen type flame retardant.
Polyol structure containing carbon-to-nitrogen double bon are as follows:
Polyhydroxy phenyl ring silicon nitrogen type flame retardant compound structure are as follows:
The preparation of modified nano oxide compound:
The mass ratio of Silane coupling agent KH550 and nano zircite is 1: 20, configures the ethanol solution containing coupling agent 4%,
Nano aluminium oxide is placed in the ethanol solution containing coupling agent, is filtered after stirring 1h, filter cake dry 2h at 95 DEG C is made and is modified
Nano zircite.
The recipe ingredient for preparing full water foamed anti-inflaming polyurethane hard foam material is as follows:
(hydroxyl value 420mgKOH/g, viscosity 2000mPa.s, HK4110G, Jining of Shandong Province Hua Kai resin are limited for polyether polyol
Company provides): 85 parts
Polyester polyol (hydroxyl value 100mgKOH/g, viscosity 3000mPa.s, HK2100, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides): 30 parts
AK-8805 (Jiangsu Maysta Chemical Co., Ltd.'s offer): 4 parts
N, N- dimethyl benzylamine (Yutai County Hai Na Environmental Protection Technology Co., Ltd): 2 parts
Trimethylolpropane (Shandong Lecron New Energy Saving Materials Co., Ltd.'s offer): 1.5 parts
Polyhydroxy phenyl ring silicon nitrogen type flame retardant (is made by oneself) according to the above method: 12 parts
Modified Nano zirconium oxide (offer of Nanjing Tian Hang new material Co., Ltd): 10 parts
Distilled water: 10 parts
Poly methylene poly phenyl poly isocyanate (offer of Henan Longhua chemical product Co., Ltd, Zhengzhou section): 150 parts
Embodiment 7:
The preparation of fire retardant:
1. under the conditions of being stirred at room temperature, 5.0g (0.041mol) parahydroxyben-zaldehyde is dissolved in shape in 75g (95ml) ethanol solution
At solution A, 4,4 '-two phenylamino of 0.0164mol2- methyl, which is dissolved in 30g (38ml) ethanol solution, forms B solution, by B at 25 DEG C
Solution is added dropwise in solution A, and time for adding control is warming up to 55 DEG C after 2h, completion of dropwise addition, is reacted 4h, is obtained one kind and contain
There is the polyol of carbon-to-nitrogen double bon;
2. under nitrogen protection, hydrosilicon trimethoxy hydrogen silane is added in the hybrid system in above-mentioned 1, simultaneously
Catalyst zinc chloride 0.25g is added, reaction mixture is warming up to 70 DEG C, 16h is reacted, is poured into 250g after being cooled to room temperature
1.5h is stirred in the petroleum ether of (386ml), solid product is obtained by filtration, then washed 5 times with cold alcohol solution, it is dry in 75 DEG C of vacuum
It is dry for 24 hours, obtain polyhydroxy phenyl ring silicon nitrogen type flame retardant.
Polyol structure containing carbon-to-nitrogen double bon are as follows:
Polyhydroxy phenyl ring silicon nitrogen type flame retardant compound structure are as follows:
The preparation of modified nano oxide compound:
The matter of Silane coupling agent KH550 and nano-cerium oxide is again than being 1: 20, ethanol solution of the configuration containing coupling agent 4%,
Nano aluminium oxide is placed in the ethanol solution containing coupling agent, is filtered after stirring 1h, filter cake dry 2h at 95 DEG C is made and is modified
Nano-cerium oxide.
The recipe ingredient for preparing full water foamed anti-inflaming polyurethane hard foam material is as follows:
(hydroxyl value 420mgKOH/g, viscosity 2000mPa.s, HK4110G, Jining of Shandong Province Hua Kai resin are limited for polyether polyol
Company provides): 75 parts
Polyester polyol (hydroxyl value 100mgKOH/g, viscosity 3000mPa.s, HK2100, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides): 30 parts
AK-8832 (Jiangsu Maysta Chemical Co., Ltd.'s offer): 4 parts
Pentamethyl-diethylenetriamine (Yutai County Hai Na Environmental Protection Technology Co., Ltd): 3 parts
Trimethylolpropane (Shandong Lecron New Energy Saving Materials Co., Ltd.'s offer): 1.5 parts
Polyhydroxy phenyl ring silicon nitrogen type flame retardant (is made by oneself) according to the above method: 12 parts
Modified nano cerium oxide (offer of Nanjing Tian Hang new material Co., Ltd): 10 parts
Distilled water: 10 parts
Poly methylene poly phenyl poly isocyanate (offer of Henan Longhua chemical product Co., Ltd, Zhengzhou section): 120 parts
Embodiment 8:
The preparation of fire retardant:
1. under the conditions of being stirred at room temperature, it is molten that 5.0g (0.041mol) parahydroxyben-zaldehyde is dissolved in formation A in 40g ethanol solution
Liquid, bis- phenylamino of 0.0205mol1,3-, which is dissolved in 25g ethanol solution, forms B solution, and B solution is added dropwise to solution A at 25 DEG C
In, time for adding control is warming up to 40 DEG C after 1h, completion of dropwise addition, reacts 2h, obtains a kind of polyhydroxy containing carbon-to-nitrogen double bon
Compound;
2. under nitrogen protection, hydrosilicon is added in the hybrid system in above-mentioned 1, while catalyst chlorination is added
Reaction mixture is warming up to 70 DEG C, reacts 8h, be poured into the petroleum ether of 175g and stir after being cooled to room temperature by zinc 0.1g
0.5h is obtained by filtration solid product, then is washed 5 times with cold alcohol solution, in 50 DEG C of vacuum drying 12h, obtains polyhydroxy phenyl ring
Silicon nitrogen type flame retardant.
Polyol structure containing carbon-to-nitrogen double bon are as follows:
Polyhydroxy phenyl ring silicon nitrogen type flame retardant compound structure are as follows:
The preparation of modified nano oxide compound:
Silane coupling agent KH550 and the mass ratio of nano iron oxide are 1: 20, configure the ethanol solution containing coupling agent 4%,
Nano aluminium oxide is placed in the ethanol solution containing coupling agent, is filtered after stirring 1h, filter cake dry 2h at 95 DEG C is made and is modified
Nano iron oxide.
The recipe ingredient for preparing full water foamed anti-inflaming polyurethane hard foam material is as follows:
Polyether polyol (hydroxyl value 430mgKOH/g, viscosity 3000mPa.s, HK8210, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides): 65 parts
Polyester polyol (hydroxyl value 280mgKOH/g, viscosity 2000mPa.s, HK2043, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides): 30 parts
AK-8811 (Jiangsu Maysta Chemical Co., Ltd.'s offer): 4 parts
1,3,5- tri- (dimethylamino-propyl) Hexahydrotriazine (Yutai County Hai Na Environmental Protection Technology Co., Ltd): 3 parts
Trimethylolpropane (Shandong Lecron New Energy Saving Materials Co., Ltd.'s offer): 1.5 parts
Polyhydroxy phenyl ring silicon nitrogen type flame retardant (is made by oneself) according to the above method: 12 parts
Modified Nano iron oxide (offer of Nanjing Tian Hang new material Co., Ltd): 8 parts
Nano ceramics: 2 parts
Distilled water: 10 parts
Poly methylene poly phenyl poly isocyanate (offer of Henan Longhua chemical product Co., Ltd, Zhengzhou section): 150 parts to full water
Foamed flame retardant polyurethane rigid foam material carries out fire-retardant and Mechanics Performance Testing, and the results are shown in Table 1:
Claims (8)
1. a kind of polyhydroxy phenyl ring silicon nitrogen type flame retardant, it is characterized in that it has following chemical structure:
Wherein R1For one kind of following structural formula:
R2For one kind of following two structural formula:
2. a kind of method for preparing polyhydroxy phenyl ring silicon nitrogen type flame retardant described in claim 1, it is characterized in that it includes following
Step:
Step 1 under the conditions of being stirred at room temperature, parahydroxyben-zaldehyde is dissolved in ethyl alcohol and forms solution A, and double amino benzene ring compounds are molten
B solution is formed in ethyl alcohol, B solution is added dropwise in solution A at 25-30 DEG C, and knot is added dropwise in 1-2h in time for adding control
It is warming up to 40-55 DEG C after beam, reacts 2-4h, obtains a kind of polyol containing carbon-to-nitrogen double bon, double aminobenzenes
Cycle compound is one of following 8 kinds of compounds:
Under step 2, nitrogen protection, silicon-containing compound is added in the reaction system in above-mentioned steps 1, while catalyst is added
Reaction mixture is warming up to 70-85 DEG C, reacts 8-16h, be poured into petroleum ether and stir after being cooled to room temperature by zinc chloride
0.5-1.5h filters out solid product, then obtains polyhydroxy phenyl ring in 50-75 DEG C of vacuum drying 12-24h with cold ethanol washing
Silicon nitrogen type flame retardant, the silicon-containing compound are one of following two kinds of compounds:
3. the method according to claim 2 for preparing polyhydroxy phenyl ring silicon nitrogen type flame retardant, it is characterized in that: the A is molten
The mass ratio of parahydroxyben-zaldehyde and ethyl alcohol is 1:8-15 in liquid, the mass ratio of double amino benzene ring compounds and ethyl alcohol in B solution
For 1:5-10, the molar ratio of double amino benzene ring compounds and parahydroxyben-zaldehyde is 1:2-2.5, double amino benzene ring compounds with contain
The molar ratio of silicon compound is 1:3-3.5, and the mass ratio of parahydroxyben-zaldehyde and petroleum ether is 1:35-50, parahydroxyben-zaldehyde
Mass ratio with zinc chloride is 1:0.02-0.05.
4. polyhydroxy phenyl ring silicon nitrogen type flame retardant described in claim 1 is in preparing full water foamed anti-inflaming polyurethane hard foam material
Application.
5. full water foamed anti-inflaming polyurethane hard foam material according to claim 4, it is characterized in that: it includes two kinds of groups of A, B
Point, by mass, the component number in component A are as follows: polyether polyol: 30-85 parts, polyester polyol: 15-30 parts, stabilizer:
2-4 parts, catalyst: 0.5-3 parts, crosslinking agent: 0.5-1.5 parts, distilled water: 3-10 parts, modified nano oxide compound: 2-10 parts, power
Benefit require 1 described in polyhydroxy phenyl ring silicon nitrogen type flame retardant: 5-12 parts;Component number in B component are as follows: polyisocyanates: 60-
150 parts.
6. full water foamed anti-inflaming polyurethane hard foam material according to claim 5, it is characterized in that: stablizing in the component A
Agent is one or more of combinations of organosilicon foam stabilizer AK-8805, AK-8811, AK-8803, AK-8832;Catalyst is three
Ethylene diamine, N, N- dimethyl cyclohexyl amine, N, N- dimethyl benzylamine, ethylenediamine, cyclohexylamine, 1,3,5- tri- (dimethylamino-propyl)
One or more of combinations of Hexahydrotriazine, pentamethyl-diethylenetriamine;Crosslinking agent is trimethylolpropane, triethanolamine, two
One or more of combinations of ethanol amine, glycerol;The polyether polyol is that polytetrahydrofuran polyol or polypropylene oxide are more
The one or more of first alcohol, hydroxyl value 420-480mgKOH/g, 25 DEG C of viscosity are 2000-6000mPa.s;Polyester polyol is rouge
The one or more of fat adoption ester polyol or aromatic polyester polyol, their hydroxyl value are 100-400mgKOH/g, 25 DEG C
Viscosity is 2000-3000mPa.s;The polyisocyanates is poly methylene poly phenyl poly isocyanate (PAPI).
7. full water foamed anti-inflaming polyurethane hard foam material according to claim 5, it is characterized in that: modified in the component A
Nano-oxide is nano-oxide through obtained by coupling agent modified processing, wherein nano-oxide is nano-titanium dioxide
(TiO2), nano silica (SiO2), nano zine oxide (ZnO), nano aluminium oxide (Al2O3), nanometer antimony pentoxide
(Sb2O5), nano zircite (ZrO2), nano-cerium oxide (CeO2), nano iron oxide (Fe2O3), one kind of nano ceramics or several
Kind combination, coupling agent is one kind of Silane coupling agent KH550 or titanate coupling agent 201, coupling agent and nano-oxide
Mass ratio is 1:15-20, first configures the ethanol solution of the 2%-4% containing coupling agent, and nano-oxide is placed in the second containing coupling agent
It in alcoholic solution, is filtered after stirring 0.5-1h, modified nano oxide compound is made in filter cake dry 2h at 80-95 DEG C.
8. the preparation method of full water foamed anti-inflaming polyurethane hard foam material described in a kind of claim 5, it is characterized in that: it is by A group
The pure and mild polyester polyol mixing high-speed stirred of polyether polyols is uniform in point, other auxiliary agents are added after mixing evenly, pass through with B component
High-pressure foam machine equipment is sufficiently mixed, by foaming machine gun head injection constant temperature sealed mold, foamed, curing demoulds one
Serial procedures obtain anti-inflaming polyurethane hard foam material.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4996255A (en) * | 1989-08-28 | 1991-02-26 | General Electric Company | Flame retardant, halogen free aromatic polycarbonate copolymer blends |
CN104277223A (en) * | 2013-07-12 | 2015-01-14 | 北京化工大学 | Macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and synthesis method and application of macromolecular flame retardant |
CN106279634A (en) * | 2016-09-06 | 2017-01-04 | 南京大学 | A kind of high-strength anti-flaming hard polyaminoester insulation material for building and preparation method thereof |
-
2017
- 2017-10-16 CN CN201710973981.1A patent/CN107722350B/en active Active
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4996255A (en) * | 1989-08-28 | 1991-02-26 | General Electric Company | Flame retardant, halogen free aromatic polycarbonate copolymer blends |
CN104277223A (en) * | 2013-07-12 | 2015-01-14 | 北京化工大学 | Macromolecular flame retardant containing three elements of phosphorus, nitrogen and silicon and synthesis method and application of macromolecular flame retardant |
CN106279634A (en) * | 2016-09-06 | 2017-01-04 | 南京大学 | A kind of high-strength anti-flaming hard polyaminoester insulation material for building and preparation method thereof |
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