CN110563765A - Synthesis method of Schiff base phosphazene double-base structure flame retardant and modified polyurethane flame retardant - Google Patents
Synthesis method of Schiff base phosphazene double-base structure flame retardant and modified polyurethane flame retardant Download PDFInfo
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- CN110563765A CN110563765A CN201910882807.5A CN201910882807A CN110563765A CN 110563765 A CN110563765 A CN 110563765A CN 201910882807 A CN201910882807 A CN 201910882807A CN 110563765 A CN110563765 A CN 110563765A
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- flame retardant
- phosphazene
- double
- schiff base
- base
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 118
- 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 109
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 150000004753 Schiff bases Chemical class 0.000 title claims abstract description 66
- 239000002262 Schiff base Substances 0.000 title claims abstract description 65
- 239000002585 base Substances 0.000 title claims abstract description 63
- 239000004814 polyurethane Substances 0.000 title claims abstract description 42
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 42
- 238000001308 synthesis method Methods 0.000 title claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000011574 phosphorus Substances 0.000 claims abstract description 19
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 16
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims abstract description 14
- -1 phosphorus nitrile Chemical class 0.000 claims abstract description 12
- 150000002825 nitriles Chemical class 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000002390 rotary evaporation Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 239000012043 crude product Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000001953 recrystallisation Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- DOZRDZLFLOODMB-UHFFFAOYSA-N 3,5-di-tert-Butyl-4-hydroxybenzaldehyde Chemical compound CC(C)(C)C1=CC(C=O)=CC(C(C)(C)C)=C1O DOZRDZLFLOODMB-UHFFFAOYSA-N 0.000 claims description 4
- CBOQJANXLMLOSS-UHFFFAOYSA-N ethyl vanillin Chemical compound CCOC1=CC(C=O)=CC=C1O CBOQJANXLMLOSS-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- PRYNJOJHKYNLIS-UHFFFAOYSA-N 6-hydroxynaphthalene-2-carbaldehyde Chemical compound C1=C(C=O)C=CC2=CC(O)=CC=C21 PRYNJOJHKYNLIS-UHFFFAOYSA-N 0.000 claims description 3
- BUMAFTGGYPBHHK-UHFFFAOYSA-N 6-oxo-1h-pyridine-3-carbaldehyde Chemical compound O=CC=1C=CC(=O)NC=1 BUMAFTGGYPBHHK-UHFFFAOYSA-N 0.000 claims description 3
- XBXFGOSIPGWNLZ-UHFFFAOYSA-N O=C1C=C(CC(C)(C)C1)C.N=C=O Chemical compound O=C1C=C(CC(C)(C)C1)C.N=C=O XBXFGOSIPGWNLZ-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000013078 crystal Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 238000010189 synthetic method Methods 0.000 claims description 3
- XLIMLVMYIYSMIQ-UHFFFAOYSA-N 4-hydroxy-2,5-dimethylbenzaldehyde Chemical compound CC1=CC(C=O)=C(C)C=C1O XLIMLVMYIYSMIQ-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 2
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 10
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 229910052799 carbon Inorganic materials 0.000 abstract description 8
- 239000000155 melt Substances 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 238000002485 combustion reaction Methods 0.000 description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 8
- 229920006264 polyurethane film Polymers 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 239000012496 blank sample Substances 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000004437 phosphorous atom Chemical group 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DZKXDEWNLDOXQH-UHFFFAOYSA-N 1,3,5,2,4,6-triazatriphosphinine Chemical compound N1=PN=PN=P1 DZKXDEWNLDOXQH-UHFFFAOYSA-N 0.000 description 1
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- GIAFURWZWWWBQT-UHFFFAOYSA-N 2-(2-aminoethoxy)ethanol Chemical compound NCCOCCO GIAFURWZWWWBQT-UHFFFAOYSA-N 0.000 description 1
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 description 1
- 206010053615 Thermal burn Diseases 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003017 phosphorus Chemical class 0.000 description 1
- 238000001394 phosphorus-31 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000004154 testing of material Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
-
- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Biochemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
- Fireproofing Substances (AREA)
Abstract
the invention discloses a synthesis method of a Schiff base phosphazene double-base structure flame retardant, which comprises the following steps of S1, reacting hexachlorocyclotriphosphazene with a compound containing hydroxyl and active carbonyl, strong base and weak acid salt and a solvent to prepare a phosphorus nitrile-containing intermediate; s2, reacting the phosphorus-containing nitrile intermediate prepared in the step S1 with an alcohol amine compound and a solvent to prepare the flame retardant containing the Schiff base phosphazene double-base structure; the synthesis method of the modified polyurethane flame retardant comprises the step of applying the prepared flame retardant with the Schiff base phosphazene double-base structure to waterborne polyurethane to prepare the waterborne polyurethane flame retardant containing the hydroxyl-terminated Schiff base phosphazene double-base structure. The flame retardant with the Schiff base phosphazene double-base structure can effectively improve the flame retardance and the anti-dripping property of the base material; the Schiff base structure contained in the modified polyurethane flame retardant structure has certain stability, the crosslinking of a melt and the formation of residual carbon can be promoted, the melt dripping resistance of the prepared flame retardant material is improved, and the nitrogen and phosphorus elements in a phosphazene ring can be flame-retardant in a synergistic manner, so that the flame retardant material has a good flame-retardant effect.
Description
Technical Field
The invention relates to the field of flame retardants, in particular to a synthesis method of a Schiff base phosphazene double-base flame retardant and a modified polyurethane flame retardant.
Background
Schiff base compounds are mainly organic compounds containing an imine or azomethine characteristic group (-RC ═ N-) and are usually prepared by condensation of an amine and an active carbonyl group. Schiff base compounds and metal complexes thereof have important application in the fields of biomedicine, catalysis, self-repairing materials, optical sensors and the like. Schiff base compounds having a relatively stable structure can modulate thermal degradation of materials by forming an ablative surface, and may have utility as an effective char-forming agent. In addition, in the combustion process, the flame retardant containing the Schiff base structure can be quickly crosslinked at high temperature, the melt viscosity and strength are improved to increase the anti-dripping property of the polymer, and the crosslinked structure is further aromatized and generates a stable carbon layer, so that the flame retardant performance is increased. Therefore, introducing Schiff base structure into different phosphorus-containing flame retardant molecules to obtain a new class of phosphorus-containing flame retardants or phosphorus-containing flame retardants with special properties is a hot spot of phosphorus-containing flame retardant research in recent years.
Hexachlorocyclotriphosphazene is a common intermediate of a swelling flame retardant, and is a compound which uses phosphorus and nitrogen atoms in single and double bonds alternately arranged as a basic skeleton, and active chlorine connected with the phosphorus atoms can perform addition reaction and nucleophilic substitution reaction so as to prepare different types of cyclic phosphazene derivatives. In the cyclotriphosphazene-based synthetic flame retardant, chlorine atoms are substituted by halogen-free groups, so that the flame retardant does not contain halogen, can release a large amount of toxic and corrosive gases in the combustion process, contains high-content nitrogen elements and phosphorus elements, and can be used as important components of the halogen-free flame retardant. At present, phosphorus-containing flame retardants become substitutes for halogen-containing flame retardants with environment-friendly and high flame retardant efficiency, and when the flame retardants are used for flame retardance of polyurethane, although the flame retardants can effectively improve the limiting oxygen index of the polyurethane, an important way for realizing flame retardance of the flame retardants is to accelerate the generation of molten drops by promoting the degradation of polymers to take away heat, so that the flame retardance of the polyurethane is realized. However, the molten droplets generated during combustion may cause secondary combustion risks, high temperature burns and other problems.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a synthesis method of a Schiff base phosphazene double-base structure flame retardant and a modified polyurethane flame retardant.
in order to solve the above problems, the present invention adopts the following technical solutions.
a synthesis method of a Schiff base phosphazene double-base structure flame retardant comprises the following steps:
S1, reacting hexachlorocyclotriphosphazene with a compound containing hydroxyl and active carbonyl, a strong base, a weak acid salt and a solvent to prepare a phosphorus-containing nitrile intermediate;
S2, reacting the intermediate containing the phosphazene prepared in the S1 with an alcohol amine compound and a solvent to prepare the flame retardant containing the Schiff base phosphazene double-base structure.
In the preparation process, intermediate with active carbonyl is generated by hexachlorocyclotriphosphazene and a compound with hydroxyl and active carbonyl, and then an alcamines compound is subjected to condensation reaction to synthesize the multifunctional flame retardant containing Schiff base/phosphazene double-base structure with the end group of hydroxyl, wherein the Schiff base and phosphazene structure in the flame retardant molecule can effectively improve the flame retardance and the anti-dripping property of the base material.
preferably, in S1, the compound containing hydroxyl and active carbonyl, the strong base, the weak acid salt, and the solvent are stirred under an oxygen-free and water-free condition until the reaction system is clear and transparent, the hexachlorocyclotriphosphazene is dissolved in the solvent, and then the solution is added dropwise into the clear and transparent reaction system, and after stirring, a crude product is obtained, and finally the crude product is subjected to rotary evaporation, water washing, recrystallization, and drying to obtain a white crystal, i.e., a phosphazene-containing intermediate.
Preferably, the compound containing hydroxyl and active carbonyl groups is one or more of p-hydroxybenzaldehyde, 3-methoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 3, 5-di-tert-butyl-4-hydroxybenzaldehyde, 2, 5-dimethyl-4-hydroxybenzaldehyde, 5- (4-hydroxypiperidine) -2-thiophenecarboxaldehyde, 6-hydroxy-2-naphthaldehyde and 2-hydroxypyridine-5-aldehyde, and the solvent is one or more of tetrahydrofuran, benzene, toluene and cyclohexane.
Preferably, in the S1, the molar ratio of hexachlorocyclotriphosphazene to the compound having a hydroxyl group and a reactive carbonyl group is 1: 6-8; the mass-volume ratio of hexachlorocyclotriphosphazene to solvent is 1 g: 10-20 ml, wherein the ratio of the compound containing hydroxyl and active carbonyl to the solvent is 1 g: 10 to 20 ml.
preferably, in S2, the phosphazene-containing intermediate obtained in S1 is mixed with a solvent uniformly, the alkanolamine compound is mixed with the solvent uniformly, the solution of the alkanolamine compound is added dropwise into the solution of the phosphazene-containing intermediate, a mixed solution is obtained after stirring, and finally, the mixed solution is subjected to rotary evaporation, washing and drying to obtain an orange solid, namely the flame retardant containing the schiff base phosphazene diradical structure.
Preferably, in the S2, the molar ratio of the intermediate containing phosphazene to the compound containing alkanolamine is 1: 1.1 to 1.2; the mass-to-volume ratio of the phosphazene-containing intermediate to the solvent was 1 g: 10-20 ml, wherein the ratio of the alcamines compound to the solvent is 1 g: 10-15 ml.
A synthetic method of a modified polyurethane flame retardant comprises the following steps:
s3, mixing polypropylene glycol 2000, 2-dimethylolpropionic acid and a catalyst for reaction, heating, adding isophorone isocyanate under stirring, further heating, adding 1, 4-butanediol, then adding acetone to adjust the viscosity of the system, and finally adding the prepared flame retardant with the Schiff base phosphazene double-base structure to obtain a prepolymer;
and S4, cooling the prepolymer, adding triethylamine, stirring, adding deionized water, performing high-speed dispersion treatment, removing acetone in vacuum, and finally preparing the aqueous polyurethane flame retardant containing the Schiff base phosphazene double-base structure, namely the modified polyurethane flame retardant.
The prepared flame retardant polyol containing the Schiff base phosphazene diradical structure can be used as a cross-linking agent to react with polyisocyanate to enable flame retardant molecules to become a part of a polyurethane molecular chain, wherein the Schiff base and phosphazene structure in the flame retardant molecules can effectively improve the flame retardance and the anti-dripping property of a base material, the mechanical property of a polyurethane film is improved, the application field of waterborne polyurethane is expanded, and the polyurethane film has good practical performance.
Preferably, in S3, the reaction system is maintained at the initial temperature of 60 ℃ and the further temperature of 80 ℃ for at least 1 hour or more after the temperature is raised.
Preferably, the amount of the flame retardant with the Schiff base phosphazene double-base structure is 6% of the total mass, the amount of the catalyst is 0.05% of the total mass, and the catalyst is dibutyltin dilaurate.
The flame retardant with the Schiff base phosphazene double-base structure is used for waterborne polyurethane to prepare the waterborne polyurethane flame retardant containing the hydroxyl end and the Schiff base phosphazene double-base structure. The strength of the polymer and the viscosity of the generated melt are sharply reduced along with the temperature increase during the combustion of the polyurethane, and the generated melt drops can cause the hazards of secondary combustion, high-temperature scald and the like. Conventional phosphorus-containing flame retardants are primarily flame retardant by accelerating the melt drip by promoting the degradation of the polymer, so as to carry away heat and flame. But the flame retardant property and the dripping behavior of the polyurethane material are intensified, so that certain potential safety hazard is brought. Aiming at the contradiction between the flame retardance and the anti-dripping property of the polyurethane. The water-based polyurethane flame retardant containing the hydroxyl-terminated Schiff base phosphazene double-base structure is prepared, has a relatively stable structure at a processing temperature, can adjust the thermal degradation of materials by forming an ablation surface in a combustion process, can be quickly crosslinked at a high temperature, improves the viscosity and strength of a melt so as to inhibit molten drops, is aromatized by a crosslinking structure and generates a stable and compact carbon layer, and realizes flame retardance by physical barrier separation of the carbon layer. The method creates a brand new way for self-carbonization flame retardance of polyurethane, and solves the contradiction between flame retardance and molten drop which cannot be solved by the traditional flame retardance method of polyurethane.
Advantageous effects
Compared with the prior art, the invention has the advantages that:
1. the flame retardant with the Schiff base phosphazene double-base structure, which is prepared by the invention, can effectively improve the flame retardance and the anti-dripping property of a base material;
2. The hydroxyl at the terminal of the modified polyurethane flame retardant prepared by the invention reacts with polyisocyanate to generate a carbamate bond, and the flame retardant molecules become a part of a macromolecular chain through a covalent bond, so that the flame retardant property is stable;
3. The Schiff base structure contained in the structure of the modified polyurethane flame retardant prepared by the invention has certain stability, the crosslinking of a melt and the formation of residual carbon can be promoted, the melt dripping resistance of the prepared flame retardant material is improved, and two elements, namely nitrogen and phosphorus in a phosphazene ring can be flame-retardant in a synergistic manner, so that the flame retardant material has a good flame retardant effect;
4. the addition amount of the prepared flame retardant containing the Schiff base phosphazene double-base structure is small when the modified flame-retardant waterborne polyurethane is prepared, so that the mechanical property of a waterborne polyurethane film is improved;
5. The preparation method is simple in preparation process and high in synthesis efficiency, and the yield of the modified polyurethane flame retardant can reach more than 90%.
Drawings
FIG. 1 is a nuclear magnetic spectrum of a Schiff base phosphazene double-base structure flame retardant in example 1;
FIG. 2 is a TGA profile of Schiff base phosphazene diradical structure flame retardant A and an aqueous polyurethane film in example 1;
FIG. 3 is a graph showing the heat release rate (HRR, a), total heat release rate (THR, b), smoke release rate (SPR, c), and total smoke release amount (TSP, d) of the polyurethane film of example 1.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention; it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and all other embodiments obtained by those skilled in the art without any inventive work based on the embodiments of the present invention belong to the protection scope of the present invention.
A synthesis method of a Schiff base phosphazene double-base structure flame retardant comprises the following steps:
s1, adding 0.16mol of p-hydroxybenzaldehyde, 0.25mol of potassium carbonate and 200ml of tetrahydrofuran into a four-mouth round-bottom flask provided with a mechanical stirrer, a condenser pipe, a constant-pressure funnel and a nitrogen protection device, introducing high-purity nitrogen into the round-bottom flask until the interior of the flask reaches an oxygen-free and anhydrous condition, and starting stirring until a reaction system is clear and transparent; dissolving 0.024mol of hexachlorocyclotriphosphazene in 100ml of tetrahydrofuran, dropwise adding the solution into a reaction container through a constant-pressure funnel, stirring and reacting for 24 hours at 65 ℃, and performing rotary evaporation, water washing, recrystallization and drying on a crude product obtained by the reaction to obtain a white crystal, namely an intermediate product, wherein the yield is 93.1%;
S2, adding the phosphorus-containing nitrile intermediate obtained in 0.02moS1 and 200ml of tetrahydrofuran into a reaction container, uniformly mixing, dissolving ethanolamine in 100ml of tetrahydrofuran, dropwise adding the mixture into the reaction container through a constant-pressure funnel, stirring and reacting for 6 hours at 55 ℃, removing the solvent from the mixture obtained by the reaction through rotary evaporation after the reaction time is up, washing the mixture with absolute ethyl alcohol for three times, and drying the obtained precipitate in a vacuum drying oven at 60 ℃ for 24 hours to obtain an orange solid, namely a target product, wherein the yield is 91.5%;
The synthesis route of the flame retardant A containing the Schiff base phosphazene diradical structure is as follows:
A synthetic method of a modified polyurethane flame retardant comprises the following steps:
S3, adding 30g of polypropylene glycol 2000, 2.8g of 2, 2-dimethylolpropionic acid and a catalyst dibutyltin dilaurate into a reactor, heating to 60 ℃, adding 19.5g of isophorone isocyanate (IPDI) under stirring, heating to 80 ℃, reacting for 2 hours, adding 1.7g of 1, 4-butanediol, continuing to react for 2 hours, adding a required flame retardant containing a Schiff base/phosphazene double-base structure, and reacting to a theoretical NCO value to obtain a prepolymer.
S4, cooling the prepolymer obtained in the step S3 to below 50 ℃, adding 2.1g of triethylamine, stirring for 15min, adding 100g of deionized water into a high-speed emulsifier, dispersing for 1h at a high speed of 1200r/min, and removing acetone in vacuum (adding a certain amount of acetone in the reaction process to adjust the viscosity of the system) to obtain the flame-retardant modified waterborne polyurethane sample.
Nuclear magnetic analysis
the experimental conditions are as follows: the flame retardant A containing the Schiff base phosphazene double-base structure is dissolved in a solvent DMSO-d6, and an AC400 type nuclear magnetic resonance instrument (Bruker company, Germany) is adopted to determine the content of a sample1H NMR spectrum.
And (3) analyzing an experimental result: FIG. 2 shows a flame retardant A containing Schiff base phosphazene double-base structure1H NMR spectrum, as indicated by the label in the figure, the peak appearing at the 3.40ppm shift is hydrogen on the methylene group attached to-N ═ CH-; the peak at 3.71ppm shift is hydrogen on methylene attached to-OH; at 4.60ppm displacement is hydrogen on the hydroxyl group; the displacement is 7.01-7.65 ppm, the proton on the benzene ring, and the displacement of 8.36ppm is assigned as hydrogen in the imine structure.31Only one single peak in the P NMR spectrum is at δ of 8.49ppm, indicating that the phosphorus atom chemical environment of the synthesized product is the same, consistent with the P atom chemical structure in the product.1H NMR and31p NMR spectrum analysis confirms the successful synthesis of the flame retardant A containing the Schiff base/phosphazene double-base structure.
Heat weight loss (TG) analysis of flame retardant A containing Schiff base phosphazene double-base structure and flame-retardant waterborne polyurethane film
The experimental conditions are as follows: thermogravimetric analysis (TG) was determined using a TGA Q500 thermogravimetric analyzer (TA, usa) under the following test conditions: the heating rate is 10 ℃/min, and the temperature range is as follows: 50 to 600 ℃ and N2And (3) performing in an atmosphere.
and (3) analyzing an experimental result: as shown in FIG. 3, the initial thermal decomposition temperature of the flame retardant A containing the Schiff base phosphazene double-base structure is 276.0 ℃, which shows that the flame retardant A has better thermal stability; the carbon residue rate is 68.5 percent at 600 ℃, and the higher carbon forming rate shows that the flame retardant A containing the Schiff base phosphazene double-base structure has good carbon forming property. When the addition amount of the flame retardant is only 6% of the total mass, the carbon residue rate of the flame-retardant waterborne polyurethane film at 600 ℃ is increased from 1.5% of a blank sample to 7.3%, which shows that in the combustion process, due to the addition of the flame retardant, more carbon layers are generated to coat the surface of the substrate, so that the heat and the transfer of combustible gas are effectively isolated, and the flame retardance of the substrate is improved.
Limited oxygen index analysis of modified waterborne polyurethane flame retardant
The experimental conditions are as follows: limiting Oxygen Index (LOI) test LOI values were determined using a HC-2C model oxygen index tester (jiangning analytical instruments factory, china) according to standard ASTM D2863-2009.
UL94 horizontal vertical burning was measured according to standard ASTM D3801-2010 on a CZF-2 horizontal vertical burning tester (Jiangning analytical instruments, China).
The cone calorimeter test was measured using an FTT cone calorimeter (FTT Co., UK). And (3) testing conditions are as follows: ISO 5660-1, spline size 100X 3mm3。
And (3) analyzing an experimental result: the addition amount of the flame retardant A containing the Schiff base/phosphazene double-base structure is 6%, the oxygen index of a water-based polyurethane sample is improved to 26.7% from 18.4% of a blank sample, and the horizontal and vertical combustion grade of UL94 reaches V-1. As can be seen from FIG. 3, the blank had a peak heat release rate of 640kW/m2And the content of the flame retardant A containing Schiff base/phosphazene double-base structure is reduced to 370kW/m2. In addition, the total heat release rate, smoke release rate and total smoke release amount are respectively 53MJ/m2to 40MJ/m2, 0.061m2From/s to 0.022m2/s, and 7.27m2/m2to 4.27m2/m2And the result shows that the flame retardant A containing the Schiff base phosphazene double-base structure is introduced to endow the waterborne polyurethane with excellent flame retardant property.
mechanical Property test
The mechanical strength of the latex film was measured using an Instron model 5567 Universal Material testing machine (Instron corporation, USA), and the sample was made into a dumbbell type standard sample bar under the conditions of a tensile rate of 50mm/min, a clamp pitch of 25mm, and a sensor sensitivity of 1 KN.
and (3) analyzing an experimental result: the addition amount of the flame retardant A containing the Schiff base/phosphazene double-base structure is 6%, the breaking strength and the breaking elongation of the waterborne polyurethane flame retardant are respectively improved to 34.76MPa and 711% from 21.82MPa and 622% of a blank sample, and the mechanical property of the modified waterborne polyurethane flame retardant is improved.
example 2
The synthesis method of the flame retardant containing the Schiff base phosphazene double-base structure comprises the following steps:
S1, adding 0.16mol of 2-hydroxypyridine-5-aldehyde, 0.25mol of potassium carbonate and 200ml of tetrahydrofuran into a four-neck round-bottom flask provided with a mechanical stirrer, a condenser tube, a constant-pressure funnel and a nitrogen protection device, introducing high-purity nitrogen into the round-bottom flask until the interior of the flask reaches an oxygen-free and water-free condition, and starting stirring until a reaction system is clear and transparent; dissolving 0.024mol of hexachlorocyclotriphosphazene in 100ml of tetrahydrofuran, dropwise adding into a reaction vessel through a constant-pressure funnel, stirring and reacting for 24 hours at 65 ℃, and carrying out rotary evaporation, water washing, recrystallization and drying on a crude product obtained by the reaction to obtain a phosphazene intermediate;
S2, adding 0.02mol of the phosphorus-containing nitrile intermediate obtained in S1 and 200ml of tetrahydrofuran into a reaction container, uniformly mixing, dissolving diglycolamine in 100ml of tetrahydrofuran, dropwise adding into the reaction container through a constant-pressure funnel, stirring and reacting for 6h at 55 ℃, after the reaction time is up, performing rotary evaporation on the obtained mixture to remove the solvent, washing with absolute ethyl alcohol for three times, and drying the obtained precipitate in a vacuum drying oven at 60 ℃ for 24h to obtain the flame retardant B containing the Schiff base/phosphazene double-base structure.
The synthesis route of the flame retardant B containing the Schiff base phosphazene double-base structure is as follows:
example 3
the synthesis method of the flame retardant containing the Schiff base phosphazene double-base structure comprises the following steps:
s1, adding 0.16mol of 5- (4-hydroxypiperidine) -2-thiophenecarboxaldehyde, 0.25mol of potassium carbonate and 200ml of tetrahydrofuran into a four-neck round-bottom flask provided with a mechanical stirrer, a condenser tube, a constant-pressure funnel and a nitrogen protection device, introducing high-purity nitrogen into the round-bottom flask until the interior of the flask reaches an oxygen-free and water-free condition, and starting stirring until a reaction system is clear and transparent; dissolving 0.024mol of hexachlorocyclotriphosphazene in 100ml of tetrahydrofuran, dropwise adding into a reaction container through a constant-pressure funnel, stirring and reacting at 65 ℃ for 24 hours, and carrying out rotary evaporation, water washing, recrystallization and drying on a crude product obtained by the reaction to obtain a phosphazene intermediate;
S2, adding the phosphorus-containing nitrile intermediate obtained by 0.02mol S1 and 200ml tetrahydrofuran into a reaction container, uniformly mixing, dissolving n-propanolamine in 100ml tetrahydrofuran, dropwise adding into the reaction container through a constant-pressure funnel, stirring and reacting for 6h at 55 ℃, after the reaction time is up, performing rotary evaporation on the obtained reaction mixture to remove the solvent, washing with absolute ethyl alcohol for three times, and drying the obtained precipitate in a vacuum drying oven at 60 ℃ for 24h to obtain the flame retardant C containing the Schiff base phosphazene diradical structure.
the synthesis route of the flame retardant C containing the Schiff base/phosphazene double-base structure is as follows:
Example 4
the synthesis method of the flame retardant containing the Schiff base phosphazene double-base structure comprises the following steps:
S1, adding 0.16mol of 6-hydroxy-2-naphthaldehyde, 0.25mol of potassium carbonate and 200ml of tetrahydrofuran into a four-neck round-bottom flask provided with a mechanical stirrer, a condenser tube, a constant-pressure funnel and a nitrogen protection device, introducing high-purity nitrogen into the round-bottom flask until the interior of the flask reaches an oxygen-free and water-free condition, and starting stirring until a reaction system is clear and transparent; dissolving 0.024mol of hexachlorocyclotriphosphazene in 100ml of tetrahydrofuran, dropwise adding into a reaction vessel through a constant-pressure funnel, stirring and reacting for 24 hours at 65 ℃, and carrying out rotary evaporation, water washing, recrystallization and drying on a crude product obtained by the reaction to obtain a phosphazene intermediate;
s2, adding the phosphorus-containing nitrile intermediate obtained in 0.02mol S1 and 200ml tetrahydrofuran into a reaction container, uniformly mixing, dissolving 2-amino-1-propanol in 100ml tetrahydrofuran, dropwise adding into the reaction container through a constant-pressure funnel, stirring and reacting for 6h at 55 ℃, after the reaction time is up, performing rotary evaporation on the obtained mixture to remove the solvent, washing with anhydrous ethanol for three times, and drying the obtained precipitate in a vacuum drying oven at 60 ℃ for 24h to obtain the flame retardant D containing the Schiff base phosphazene double-base structure.
The synthesis route of the flame retardant D containing the Schiff base phosphazene double-base structure is as follows:
The foregoing is illustrative of the preferred embodiments of the present invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the inventive concept as defined by the appended claims, as modified by the teachings or knowledge of the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A synthesis method of a Schiff base phosphazene double-base structure flame retardant is characterized by comprising the following steps: the method comprises the following steps:
S1, reacting hexachlorocyclotriphosphazene with a compound containing hydroxyl and active carbonyl, a strong base, a weak acid salt and a solvent to prepare a phosphorus-containing nitrile intermediate;
s2, reacting the intermediate containing the phosphazene prepared in the S1 with an alcohol amine compound and a solvent to prepare the flame retardant containing the Schiff base phosphazene double-base structure.
2. The synthesis method of the Schiff base phosphazene double-base structure flame retardant according to claim 1, which is characterized in that: in the S1, firstly, a compound containing hydroxyl and an active carbonyl, a strong base and a weak acid salt and a solvent are stirred under the oxygen-free and water-free conditions until a reaction system is clear and transparent, then hexachlorocyclotriphosphazene is dissolved in the solvent and is dripped into the clear and transparent reaction system, a crude product is prepared after stirring, and finally, the crude product is subjected to rotary evaporation, water washing, recrystallization and drying to obtain a white crystal, namely a phosphazene-containing intermediate.
3. the synthesis method of the Schiff base phosphazene double-base structure flame retardant according to claim 2, characterized in that: the compound containing hydroxyl and active carbonyl is one or more of p-hydroxybenzaldehyde, 3-methoxy-4-hydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, 3, 5-di-tert-butyl-4-hydroxybenzaldehyde, 2, 5-dimethyl-4-hydroxybenzaldehyde, 5- (4-hydroxypiperidine) -2-thiophenecarboxaldehyde, 6-hydroxy-2-naphthaldehyde and 2-hydroxypyridine-5-aldehyde, and the solvent is one or more of tetrahydrofuran, benzene, toluene and cyclohexane.
4. The synthesis method of the Schiff base phosphazene double-base structure flame retardant according to claim 2, characterized in that: in the S1, the molar ratio of the hexachlorocyclotriphosphazene to the compound having a hydroxyl group and an active carbonyl group is 1: 6-8; the mass-volume ratio of hexachlorocyclotriphosphazene to solvent is 1 g: 10-20 ml, wherein the ratio of the compound containing hydroxyl and active carbonyl to the solvent is 1 g: 10 to 20 ml.
5. The synthesis method of the Schiff base phosphazene double-base structure flame retardant according to claim 1, which is characterized in that: in the S2, the phosphorus-containing nitrile intermediate prepared in the S1 is uniformly mixed with a solvent, the alcohol amine compound is uniformly mixed with the solvent, the alcohol amine compound solution is dropwise added into the phosphazene intermediate-containing solution, a mixed solution is obtained after stirring, and finally, the mixed solution is subjected to rotary evaporation, washing and drying to obtain an orange solid, namely the flame retardant containing the Schiff base phosphazene diradical structure.
6. The synthesis method of the Schiff base phosphazene double-base structure flame retardant according to claim 1, which is characterized in that: in the S2, the molar ratio of the phosphorus-containing nitrile intermediate to the alkanolamine-bearing compound is 1: 1.1 to 1.2; the mass-to-volume ratio of the phosphazene-containing intermediate to the solvent was 1 g: 10-20 ml, wherein the ratio of the alcohol amine compound to the solvent is 1 g: 10-15 ml.
7. A synthetic method of a modified polyurethane flame retardant is characterized by comprising the following steps: the method comprises the following steps:
S3, mixing polypropylene glycol 2000, 2-dimethylolpropionic acid and a catalyst for reaction, heating, adding isophorone isocyanate under stirring, further heating, adding 1, 4-butanediol, then adding acetone to adjust the viscosity of the system, and finally adding the Schiff base phosphazene double-base structure flame retardant prepared according to any one of claims 1-6 to obtain a prepolymer;
and S4, cooling the prepolymer, adding triethylamine, stirring, adding deionized water for high-speed dispersion treatment, removing acetone in vacuum, and finally obtaining the aqueous polyurethane flame retardant containing the Schiff base phosphazene double-base structure, namely the modified polyurethane flame retardant.
8. The method for synthesizing the modified polyurethane flame retardant of claim 7, wherein the method comprises the following steps: in S3, in the reaction system, the initial temperature rise is 60 ℃, the further temperature rise is 80 ℃, and the reaction time is maintained for at least 1 hour or more after the temperature rise.
9. the method for synthesizing the modified polyurethane flame retardant of claim 7, wherein the method comprises the following steps: the amount of the Schiff base phosphazene double-base structure flame retardant is 6% of the total mass, the amount of the catalyst is 0.05% of the total mass, and the catalyst is dibutyltin dilaurate.
10. the application of the flame retardant with the Schiff base phosphazene double-base structure is characterized in that: the Schiff base phosphazene double-base structure flame retardant prepared by any one of claims 1 to 6 is used for aqueous polyurethane to prepare an aqueous polyurethane flame retardant containing a hydroxyl-terminated Schiff base phosphazene double-base structure.
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