CN107722350A - 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
- Publication number
- CN107722350A CN107722350A CN201710973981.1A CN201710973981A CN107722350A CN 107722350 A CN107722350 A CN 107722350A CN 201710973981 A CN201710973981 A CN 201710973981A CN 107722350 A CN107722350 A CN 107722350A
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- Prior art keywords
- nano
- parts
- flame retardant
- oxide
- solution
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 66
- 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 44
- 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 40
- 239000006261 foam material Substances 0.000 title claims description 27
- 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
- 150000001875 compounds Chemical class 0.000 claims abstract description 28
- 239000006260 foam Substances 0.000 claims abstract description 18
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 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
- 101710130081 Aspergillopepsin-1 Proteins 0.000 claims abstract description 13
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 13
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 98
- 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 31
- 239000007822 coupling agent Substances 0.000 claims description 30
- 150000003077 polyols Chemical class 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
- -1 poly methylene Polymers 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 20
- 229920001451 polypropylene glycol Polymers 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 229920005862 polyol Polymers 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 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 claims description 12
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Chemical compound O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-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
- 125000002490 anilino group Chemical group [H]N(*)C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229920006389 polyphenyl polymer Polymers 0.000 claims description 10
- 239000000376 reactant Substances 0.000 claims description 10
- 239000012265 solid product Substances 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical group CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-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
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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 class CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002105 nanoparticle Substances 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
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 239000005543 nano-size silicon particle Substances 0.000 claims description 3
- JQYOCVPEXWBLGO-UHFFFAOYSA-N [N].[Si].[P] Chemical compound [N].[Si].[P] JQYOCVPEXWBLGO-UHFFFAOYSA-N 0.000 claims description 2
- 229920003232 aliphatic polyester Polymers 0.000 claims description 2
- 150000001555 benzenes Chemical class 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 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
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- OYWRDHBGMCXGFY-UHFFFAOYSA-N 1,2,3-triazinane Chemical compound C1CNNNC1 OYWRDHBGMCXGFY-UHFFFAOYSA-N 0.000 claims 1
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims 1
- 101000598921 Homo sapiens Orexin Proteins 0.000 claims 1
- 101001123245 Homo sapiens Protoporphyrinogen oxidase Proteins 0.000 claims 1
- 102100029028 Protoporphyrinogen oxidase Human genes 0.000 claims 1
- 230000001476 alcoholic effect Effects 0.000 claims 1
- 150000003377 silicon compounds Chemical class 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 20
- 239000012153 distilled water Substances 0.000 abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 74
- 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
- 239000004615 ingredient Substances 0.000 description 9
- 230000007613 environmental effect Effects 0.000 description 8
- 150000004754 hydrosilicons Chemical class 0.000 description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 7
- 229910000077 silane Inorganic materials 0.000 description 7
- 229920005830 Polyurethane Foam Polymers 0.000 description 6
- 239000004088 foaming agent Substances 0.000 description 6
- 239000011496 polyurethane foam Substances 0.000 description 6
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 230000000694 effects Effects 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002485 combustion reaction Methods 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
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 2
- 230000000979 retarding effect Effects 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 150000003457 sulfones Chemical class 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 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
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-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
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 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
- 230000000254 damaging effect 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
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 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
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 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
- 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
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002861 polymer material Substances 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
- 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 retardant, it is characterized in that it has following chemical constitution：Wherein R1For following structural formula or its analog：Wherein R2One kind or its analog for following structural formula：With the polyhydroxy phenyl ring silicon nitrogen type flame retardant of the present invention, using PPG, PEPA, polyisocyanates, catalyst, stabilizer, crosslinking agent, modified nano oxide compound, fire retardant, distilled water as primary raw material, blended, high-speed stirred, foaming, curing, obtain full water foamed flame retarded rigid polyurethane material.The full water foamed flame retardant polyurethane rigid foam of gained has higher mechanical property and fire resistance, 58.5~64.5kg/m of density3, 0.405~0.45MPa of compressive strength, draw 0.53~0.68MPa of Zhong Qiangdu, limited 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 technology
Rigid polyurethane material is one of current most popular high polymer material, has a low-density, and high specific strength is excellent
Different anti-wear performance, low thermal conductivity, and excellent damping sound absorption qualities etc..The shortcomings that hard polyurethane foam is inflammable and resistance to height
Warm poor performance, contact burning things which may cause a fire disaster can produce flame immediately, and the life and property to the mankind bring huge threat, are applied to
Generate great limitation.Reactive flame retardant participates in polymerisation in polyurethane building-up process and is attached to ignition-proof element
On material molecule main chain or side chain, so that the polyurethane material prepared has fire resistance, this based flame retardant and matrix material
Expect that compatibility is good, flame retarding efficiency is high.Phosphorus system, silicon-series five-retardant have high flame retarding efficiency, flame retardant effect lasting stability and cost low
Etc. advantage, and the compound of aromatic structure or heterocycle structure has the rigid effect of reinforcing material strand 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, and but the fire resistance of material is not had greatly improved.
The preparation of hard polyurethane foam typically using low boiling 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 poisonous, inflammable and explosive, and have damaging effect to environment.The foam process using water as foaming agent is opened in recent years
Beginning is widely studied, water and isocyanates reaction generation CO2As foaming agent, ozone damped expoential (ODP) is 0, and
Foam process is more simple and safe.But compared with physical blowing system, the full water foamed material prepared there is low intensity,
The shortcomings of dimensional stability is poor, foams embrittlement 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 incorporated into the molecular structure of polyurethane material by the present invention, in combination with rigid heat resistant
Benzene ring structure, enhance the fire resistance 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, hard polyurethane foam is prepared using full water foamed system, further will be modified
Nano-oxide is added thereto, largely overcome the low full water foamed rigid poly urethanes strength of materials, poor dimensional stability,
The shortcomings of foams embrittlement.
The content of the invention
In order to solve above mentioned problem existing for prior art, the invention provides a kind of full water foamed anti-inflaming polyurethane hard foam
Material and preparation method thereof.The method that one aspect of the present invention utilizes chemical constitution MOLECULE DESIGN, prepares polyhydroxy phenyl ring silicon nitrogen
Flame retardant, the presence of silicon N structure and benzene radicals enhance the fire resistance and heat resistance of material, on the other hand, use
The water that ODP values are zero introduces modified nano oxide compound as foaming agent, effectively improves the drawing Zhong Qiangdu of material foams body, wear-resisting
Property and ageing resistace, and cause foams be not easy embrittlement.In order to realize 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 constitution：
Wherein R1For one kind of following structural formula：
R2For one kind of following structural formula：
A kind of method for preparing above-mentioned polyhydroxy phenyl ring silicon nitrogen type flame retardant, it is reacted as follows：
It comprises the following steps：
Step 1, under the conditions of being stirred at room temperature, parahydroxyben-zaldehyde is dissolved in ethanol and forms solution A, double aminobenzene cyclisation are closed
Thing, which is dissolved in ethanol, 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
40-55 DEG C is warming up to after adding end, 2-4h is reacted, obtains a kind of polyol containing carbon-to-nitrogen double bon, described double ammonia
Base benzene ring compound is one kind in 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 add and urge
Agent zinc chloride, reactant mixture is warming up to 70-85 DEG C, reacts 8-16h, be cooled to after room temperature to be poured into petroleum ether and stir
0.5-1.5h is mixed, filters out solid product, then is washed with cold ethanol, 12-24h is dried in vacuo in 50-75 DEG C, obtains polyhydroxy benzenes
Ring silicon nitrogen type flame retardant, described silicon-containing compound are one kind in following two kinds of compounds：
The above-mentioned method for preparing polyhydroxy phenyl ring Phosphorus-nitrogen flame retardant, parahydroxyben-zaldehyde and second in described solution A
The mass ratio of alcohol is 1：8-15, the mass ratio of double amino benzene ring compounds and ethanol is 1 in B solution：5-10, double aminobenzene cyclisation
The mol ratio of compound and parahydroxyben-zaldehyde is 1: 2-2.5, and the mol 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。
Application of the above-mentioned polyhydroxy phenyl ring silicon nitrogen type flame retardant in full water foamed anti-inflaming polyurethane hard foam material is prepared.
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 is：PPG：30-85 parts, PEPA：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, the resistance of above-mentioned polyhydroxy benzenes silicon phosphorus-nitrogen type
Fire agent：5-12 parts；Component number in B component is：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
8805th, AK-8811, AK-8803, AK-8832 one or more of combinations；Catalyst is triethylene diamine, N, N- dimethyl
Cyclohexylamine, N, N- dimethyl benzylamines, 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, glycerine one kind or
Several combinations；The PPG is the one or more of polytetrahydrofuran polyol or polyoxypropylene polyol, hydroxyl
It is 2000-6000mPa.s (25 DEG C) to be worth for 420-480mgKOH/g, viscosity；PEPA 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 oxide (TiO2), nano silicon (SiO2), receive
Rice zinc oxide (ZnO), nano aluminium oxide (Al2O3), nanometer antimony pentoxide (Sb2O5), nano zircite (ZrO2), it is nano oxidized
Cerium (CeO2), nano-sized 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 is 1: 15-20, and first configuration contains coupling agent
2%-4% ethanol solution, nano-oxide is placed in the ethanol solution containing coupling agent, filtered after stirring 0.5-1h, filter cake
2h is dried at 80-95 DEG C, modified nano oxide compound is made.
A kind of preparation method of above-mentioned full water foamed anti-inflaming polyurethane hard foam material, it be by PPG in component A and
PEPA mixing high-speed stirred is uniform, adds after other auxiliary agents stir, is entered with B component by high-pressure foam machine equipment
Row is sufficiently mixed, and is injected by foaming machine gun head in constant temperature sealed mold, and 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 a kind of silicon N structure fire retardant is synthesized
Urethane rigid foam.The ignition-proof elements such as silicon, nitrogen are incorporated into the molecular structure of polyurethane material, in combination with rigid heat resistant benzene
Ring structure, strengthen the fire resistance and molecule chain rigidity of rigid polyurethane material.Abandon physical blowing agent fluorochlorohydrocarbon class chemical combination
The use of thing, hard polyurethane foam is prepared using full water foamed system, is further added thereto modified nano oxide compound,
The shortcomings of largely overcoming the low full water foamed rigid poly urethanes strength of materials, poor dimensional stability, foams embrittlement.This
Invention has the beneficial effect that：
1. the present invention prepares flame retardant polyurethane rigid foam, without harmful elements such as halogens, avoid in combustion
Toxic gas and a large amount of smog are produced, and contains the good benzene ring structure of heat endurance and fire-retardant silicon nitrogen knot in molecular chain structure
Structure, enhance the heat endurance and fire resistance of hard polyaminoester；
2. the present invention is based on full water foamed flame retardant polyurethane rigid foam, modified nano oxide compound is introduced wherein,
The shortcomings 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 has higher mechanical property and fire resistance, 58.5~64.5kg/m of density3, compressive strength
0.405~0.45MPa, draw 0.53~0.68MPa of Zhong Qiangdu, limited oxygen index 285~345%.
Embodiment
Polyhydroxy phenyl ring silicon nitrogen type flame retardant of the invention is illustrated using embodiment below and one kind is full water foamed
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 formed, to be limited.
A kind of full water foamed anti-inflaming polyurethane hard foam material of the present 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 molds of the A, B component after being sufficiently mixed, through hair
A series of processes such as bubble, curing, the 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
Into solution A, 3.0g (0.0164mol) 4,4 '-benzidine, 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, reactant mixture is warming up to 85 DEG C, 16h is reacted, 250g is poured into after being cooled to room temperature
1.5h is stirred in the petroleum ether of (386ml), is filtrated to get solid product, then is washed 5 times with cold alcohol solution, is done in 75 DEG C of vacuum
Dry 24h, obtain polyhydroxy phenyl ring silicon nitrogen type flame retardant.
Polyol structure containing carbon-to-nitrogen double bon is：
Polyhydroxy phenyl ring silicon nitrogen type flame retardant compound structure is：
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, filtered after stirring 1h, filter cake dries 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：
PPG (hydroxyl value 470mgKOH/g, viscosity 3000mPa.s, HK4110, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides)：85 parts
PEPA (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 part
Polyhydroxy phenyl ring silicon nitrogen type flame retardant (is made by oneself) as stated above：12 parts
Modified nano-alumina (offer of Nanjing Tian Hang new materials Co., Ltd)：10 parts
Distilled water：10 parts
Poly methylene poly phenyl poly isocyanate (offer of Henan Longhua chemical product Co., Ltd of 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 solutions
Liquid, 0.0205mol3,3 '-dimethoxy 4,4 '-benzidine, which is dissolved in 25g ethanol solutions, 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, reacts 2h, obtains 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, reactant 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, is filtrated to get solid product, then is washed 5 times with cold alcohol solution, 12h is dried in vacuo in 50 DEG C, obtains
To polyhydroxy phenyl ring silicon nitrogen type flame retardant.
Polyol structure containing carbon-to-nitrogen double bon is：
Polyhydroxy phenyl ring silicon nitrogen type flame retardant compound structure is：
The preparation of modified nano oxide compound：
The mass ratio of titanate coupling agent 201 and nano titanium oxide is 1: 15, and it is molten to configure the ethanol containing coupling agent 2%
Liquid, nano titanium oxide being placed in the ethanol solution containing coupling agent, filtered after stirring 0.5h, filter cake dries 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：
PPG (hydroxyl value 480mgKOH/g, viscosity 6000mPa.s, HK8205, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides)：30 parts
PEPA (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) as stated above：5 parts
Modified nano-titanium dioxide (offer of Nanjing Tian Hang new materials Co., Ltd)：2 parts
Distilled water：3 parts
Poly methylene poly phenyl poly isocyanate (offer of Henan Longhua chemical product Co., Ltd of 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
Into solution A, 0.0164mol3,3 '-diaminobenzene sulfone, which is 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, reacts 3h, obtains 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, reactant mixture is warming up to 85 DEG C, 10h is reacted, 250g is poured into after being cooled to room temperature
1.5h is stirred in the petroleum ether of (386ml), is filtrated to get solid product, then is washed 5 times with cold alcohol solution, is done in 75 DEG C of vacuum
Dry 24h, obtain polyhydroxy phenyl ring silicon nitrogen type flame retardant.
Polyol structure containing carbon-to-nitrogen double bon is：
Polyhydroxy phenyl ring silicon nitrogen type flame retardant compound structure is：
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, filtered after stirring 1h, filter cake dries 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 PPG
Company provides)：55 parts
PEPA (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 part
Polyhydroxy phenyl ring silicon nitrogen type flame retardant (is made by oneself) as stated above：12 parts
Modified nano zinc oxide (offer of Nanjing Tian Hang new materials Co., Ltd)：10 parts
Distilled water：10 parts
Poly methylene poly phenyl poly isocyanate (offer of Henan Longhua chemical product Co., Ltd of 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
Into solution A, 0.0164mol4,4 '-diaminobenzene sulfone, which is 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, reacts 2h, obtains 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, reactant mixture is warming up to 80 DEG C, 16h is reacted, 250g is poured into after being cooled to room temperature
1.5h is stirred in the petroleum ether of (386ml), is filtrated to get solid product, then is washed 5 times with cold alcohol solution, is done in 75 DEG C of vacuum
Dry 20h, obtain polyhydroxy phenyl ring silicon nitrogen type flame retardant.
Polyol structure containing carbon-to-nitrogen double bon is：
Polyhydroxy phenyl ring silicon nitrogen type flame retardant compound structure is：
The preparation of modified nano oxide compound：
The mass ratio of Silane coupling agent KH550 and nano silicon is 1: 15, and it is molten to configure the ethanol containing coupling agent 3%
Liquid, nano aluminium oxide is placed in the ethanol solution containing coupling agent, filtered after stirring 1h, filter cake dries 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：
PPG (hydroxyl value 430mgKOH/g, viscosity 3000mPa.s, HK8210, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides)：65 parts
PEPA (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
Glycerine (Shandong Lecron New Energy Saving Materials Co., Ltd.'s offer)：1.5 part
Polyhydroxy phenyl ring silicon nitrogen type flame retardant (is made by oneself) as stated above：12 parts
Modified manometer silicon dioxide (offer of Nanjing Tian Hang new materials Co., Ltd)：10 parts
Distilled water：10 parts
Poly methylene poly phenyl poly isocyanate (offer of Henan Longhua chemical product Co., Ltd of 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
Into solution A, 0.0164mol4,4 '-diamino-benzene is dissolved in 30g (38ml) ethanol solution and forms 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, reactant mixture is warming up to 85 DEG C, 16h is reacted, 250g is poured into after being cooled to room temperature
1.5h is stirred in the petroleum ether of (386ml), is filtrated to get solid product, then is washed 5 times with cold alcohol solution, is done in 75 DEG C of vacuum
Dry 24h, obtain polyhydroxy phenyl ring silicon nitrogen type flame retardant.
Polyol structure containing carbon-to-nitrogen double bon is：
Polyhydroxy phenyl ring silicon nitrogen type flame retardant compound structure is：
The preparation of modified nano oxide compound：
The mass ratio of titanate coupling agent 201 and nanometer antimony pentoxide is 1：20, it is molten to configure the ethanol containing coupling agent 4%
Liquid, nano aluminium oxide is placed in the ethanol solution containing coupling agent, filtered after stirring 1h, filter cake dries 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：
PPG (hydroxyl value 470mgKOH/g, viscosity 3000mPa.s, HK4110, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides)：75 parts
PEPA (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 part
Polyhydroxy phenyl ring silicon nitrogen type flame retardant (is made by oneself) as stated above：10 parts
Modified Nano antimony pentoxide (offer of Nanjing Tian Hang new materials Co., Ltd)：10 parts
Distilled water：10 parts
Poly methylene poly phenyl poly isocyanate (offer of Henan Longhua chemical product Co., Ltd of 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
Into solution A, 0.0164mol3, the phenylamino of 3 ' dimethyl 4,4 '-two, 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, reactant mixture is warming up to 85 DEG C, 10h is reacted, 250g is poured into after being cooled to room temperature
1.5h is stirred in the petroleum ether of (386m1), is filtrated to get solid product, then is washed 5 times with cold alcohol solution, is done in 75 DEG C of vacuum
Dry 24h, obtain polyhydroxy phenyl ring silicon nitrogen type flame retardant.
Polyol structure containing carbon-to-nitrogen double bon is：
Polyhydroxy phenyl ring silicon nitrogen type flame retardant compound structure is：
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, filtered after stirring 1h, filter cake dries 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 PPG
Company provides)：85 parts
PEPA (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 part
Polyhydroxy phenyl ring silicon nitrogen type flame retardant (is made by oneself) as stated above：12 parts
Modified Nano zirconium oxide (offer of Nanjing Tian Hang new materials Co., Ltd)：10 parts
Distilled water：10 parts
Poly methylene poly phenyl poly isocyanate (offer of Henan Longhua chemical product Co., Ltd of 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
Into solution A, the phenylamino of 0.0164mol2- methyl 4,4 '-two, 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, reacts 4h, obtains 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, reactant mixture is warming up to 70 DEG C, 16h is reacted, 250g is poured into after being cooled to room temperature
1.5h is stirred in the petroleum ether of (386ml), is filtrated to get solid product, then is washed 5 times with cold alcohol solution, is done in 75 DEG C of vacuum
Dry 24h, obtain polyhydroxy phenyl ring silicon nitrogen type flame retardant.
Polyol structure containing carbon-to-nitrogen double bon is：
Polyhydroxy phenyl ring silicon nitrogen type flame retardant compound structure is：
The preparation of modified nano oxide compound：
The matter of Silane coupling agent KH550 and nano-cerium oxide again than for 1: 20, configuring the ethanol solution containing coupling agent 4%,
Nano aluminium oxide is placed in the ethanol solution containing coupling agent, filtered after stirring 1h, filter cake dries 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 PPG
Company provides)：75 parts
PEPA (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 part
Polyhydroxy phenyl ring silicon nitrogen type flame retardant (is made by oneself) as stated above：12 parts
Modified nano cerium oxide (offer of Nanjing Tian Hang new materials Co., Ltd)：10 parts
Distilled water：10 parts
Poly methylene poly phenyl poly isocyanate (offer of Henan Longhua chemical product Co., Ltd of 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 solutions
Liquid, the phenylamino of 0.0205mol1,3- bis-, which is dissolved in 25g ethanol solutions, forms B solution, and B solution is added dropwise into 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 add catalyst chlorination
Zinc 0.1g, reactant mixture is warming up to 70 DEG C, reacts 8h, be cooled to after room temperature to be poured into 175g petroleum ether and stir
0.5h, solid product is filtrated to get, then is washed 5 times with cold alcohol solution, be dried in vacuo 12h in 50 DEG C, obtain polyhydroxy phenyl ring
Silicon nitrogen type flame retardant.
Polyol structure containing carbon-to-nitrogen double bon is：
Polyhydroxy phenyl ring silicon nitrogen type flame retardant compound structure is：
The preparation of modified nano oxide compound：
The mass ratio of Silane coupling agent KH550 and nano-sized iron oxide is 1: 20, configures the ethanol solution containing coupling agent 4%,
Nano aluminium oxide is placed in the ethanol solution containing coupling agent, filtered after stirring 1h, filter cake dries 2h at 95 DEG C, is made and is modified
Nano-sized iron oxide.
The recipe ingredient for preparing full water foamed anti-inflaming polyurethane hard foam material is as follows：
PPG (hydroxyl value 430mgKOH/g, viscosity 3000mPa.s, HK8210, the limited public affairs of Jining of Shandong Province Hua Kai resin
Department provides)：65 parts
PEPA (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 part
Polyhydroxy phenyl ring silicon nitrogen type flame retardant (is made by oneself) as stated above：12 parts
Modified Nano iron oxide (offer of Nanjing Tian Hang new materials 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 of Zhengzhou section)：150 parts to full water
Foamed flame retardant polyurethane rigid foam material carries out fire-retardant and Mechanics Performance Testing, as a result as shown in table 1：
Claims (8)
- A kind of 1. polyhydroxy phenyl ring silicon nitrogen type flame retardant, it is characterized in that it has following chemical constitution：Wherein R1For one kind of following structural formula：R2For one kind of following two structural formulas：
- A kind of 2. method of the polyhydroxy phenyl ring silicon nitrogen type flame retardant prepared described in claim 1, it is characterized in that it is including following Step：Step 1, under the conditions of being stirred at room temperature, parahydroxyben-zaldehyde is dissolved in ethanol and forms solution A, double amino benzene ring compounds are molten B solution is formed in ethanol, B solution is added dropwise in solution A at 25-30 DEG C, time for adding control is in 1-2h, dropwise addition knot 40-55 DEG C is warming up to after beam, 2-4h is reacted, obtains a kind of polyol containing carbon-to-nitrogen double bon, described double aminobenzenes Cycle compound is one kind in 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 add catalyst Zinc chloride, reactant mixture is warming up to 70-85 DEG C, reacts 8-16h, be cooled to after room temperature to be poured into petroleum ether and stir 0.5-1.5h, solid product is filtered out, then washed with cold ethanol, be dried in vacuo 12-24h in 50-75 DEG C, obtain polyhydroxy phenyl ring Silicon nitrogen type flame retardant, described silicon-containing compound are one kind in 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：Described A is molten The mass ratio of parahydroxyben-zaldehyde and ethanol is 1: 8-15 in liquid, the mass ratio of double amino benzene ring compounds and ethanol in B solution For 1: 5-10, the mol ratio of double amino benzene ring compounds and parahydroxyben-zaldehyde is 1: 2-2.5, and double amino benzene ring compounds are with containing The mol 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. the polyhydroxy phenyl ring silicon nitrogen type flame retardant described in claim 1 is in full water foamed anti-inflaming polyurethane hard foam material is prepared 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 is：PPG：30-85 parts, PEPA：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, on The polyhydroxy benzenes silicon Phosphorus-nitrogen flame retardant stated：5-12 parts；Component number in B component is：Polyisocyanates：60-150 parts.
- 6. full water foamed anti-inflaming polyurethane hard foam material according to claim 4, it is characterized in that：It is stable in the component A Agent is organosilicon foam stabilizer AK-8805, AK-8811, AK-8803, AK-8832 one or more of combinations；Catalyst is three Ethylene diamine, N, N- dimethyl cyclohexyl amines, N, N- dimethyl benzylamines, ethylenediamine, cyclohexylamine, 1,3,5- tri- (dimethylamino-propyls) One or more of combinations of Hexahydrotriazine, pentamethyl-diethylenetriamine；Crosslinking agent is trimethylolpropane, triethanolamine, two One or more of combinations of monoethanolamine, glycerine；The PPG is that polytetrahydrofuran polyol or PPOX are more The one or more of first alcohol, hydroxyl value 420-480mgKOH/g, viscosity are 2000-6000mPa.s (25 DEG C)；PEPA is The one or more of aliphatic polyester polyols or aromatic polyester polyol, their hydroxyl value are 100-400mgKOH/g, are glued Spend for 2000-3000mPa.s (25 DEG C)；The polyisocyanates is poly methylene poly phenyl poly isocyanate (PAPI).
- 7. full water foamed anti-inflaming polyurethane hard foam material according to claim 4, it is characterized in that：It is modified in the component A Nano-oxide is nano-oxide through obtained by coupling agent modified processing, wherein nano-oxide is nano titanium oxide (TiO2), nano silicon (SiO2), nano zine oxide (ZnO), nano aluminium oxide (Al2O3), nanometer antimony pentoxide (Sb2O5), nano zircite (ZrO2), nano-cerium oxide (CeO2), nano-sized 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 into the second containing coupling agent In alcoholic solution, filtered after stirring 0.5-1h, filter cake dries 2h at 80-95 DEG C, and modified nano oxide compound is made.
- 8. a kind of preparation method of the full water foamed anti-inflaming polyurethane hard foam material described in claim 4, it is characterized in that：It is by A groups PPG and PEPA mixing high-speed stirred are uniform in point, add after other auxiliary agents stir, pass through with B component High-pressure foam machine equipment is sufficiently mixed, and is injected by foaming machine gun head in constant temperature sealed mold, foamed, curing, demoulding etc. A series of processes obtain anti-inflaming polyurethane hard foam material.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503794A (en) * | 2018-11-13 | 2019-03-22 | 江苏奥斯佳材料科技股份有限公司 | A kind of polyurethane rigid foam composition and polyurethane rigid foam material and preparation method thereof |
| CN110964309A (en) * | 2019-12-11 | 2020-04-07 | 泉州玺堡家居科技有限公司 | High-hardness sponge and processing technology thereof |
| CN115262022A (en) * | 2022-08-22 | 2022-11-01 | 安徽龙航电缆有限公司 | Aviation non-metal braided sleeve |
| CN115785372A (en) * | 2022-11-14 | 2023-03-14 | 天津爱德加科技有限公司 | High-flexibility compression-resistant full-water open-cell rigid polyurethane foam and preparation method thereof |
| CN116675830A (en) * | 2023-04-24 | 2023-09-01 | 广东豪美新材股份有限公司 | Buffering energy-absorbing material |
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
Patent 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 |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109503794A (en) * | 2018-11-13 | 2019-03-22 | 江苏奥斯佳材料科技股份有限公司 | A kind of polyurethane rigid foam composition and polyurethane rigid foam material and preparation method thereof |
| CN113501924A (en) * | 2018-11-13 | 2021-10-15 | 江苏奥斯佳材料科技股份有限公司 | Polyurethane rigid foam thermal insulation material |
| CN110964309A (en) * | 2019-12-11 | 2020-04-07 | 泉州玺堡家居科技有限公司 | High-hardness sponge and processing technology thereof |
| CN115262022A (en) * | 2022-08-22 | 2022-11-01 | 安徽龙航电缆有限公司 | Aviation non-metal braided sleeve |
| CN115785372A (en) * | 2022-11-14 | 2023-03-14 | 天津爱德加科技有限公司 | High-flexibility compression-resistant full-water open-cell rigid polyurethane foam and preparation method thereof |
| CN115785372B (en) * | 2022-11-14 | 2023-09-26 | 天津爱德加科技有限公司 | High-flexibility compression-resistant all-water open-cell rigid polyurethane foam and preparation method thereof |
| CN116675830A (en) * | 2023-04-24 | 2023-09-01 | 广东豪美新材股份有限公司 | Buffering energy-absorbing material |
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