CN106986896A - Star-like boron phosphazene derivative expansion type flame retardant and preparation method thereof - Google Patents
Star-like boron phosphazene derivative expansion type flame retardant and preparation method thereof Download PDFInfo
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- CN106986896A CN106986896A CN201710145711.1A CN201710145711A CN106986896A CN 106986896 A CN106986896 A CN 106986896A CN 201710145711 A CN201710145711 A CN 201710145711A CN 106986896 A CN106986896 A CN 106986896A
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- boron
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- flame retardant
- expansion type
- type flame
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 83
- 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 42
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 35
- -1 boron phosphazene derivative Chemical class 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 104
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000013067 intermediate product Substances 0.000 claims abstract description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 24
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000011010 flushing procedure Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000741 silica gel Substances 0.000 claims abstract description 8
- 229910002027 silica gel Inorganic materials 0.000 claims abstract description 8
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 239000003208 petroleum Substances 0.000 claims description 9
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 7
- 238000005903 acid hydrolysis reaction Methods 0.000 claims description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical class CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 claims description 6
- ZSTLPJLUQNQBDQ-UHFFFAOYSA-N azanylidyne(dihydroxy)-$l^{5}-phosphane Chemical compound OP(O)#N ZSTLPJLUQNQBDQ-UHFFFAOYSA-N 0.000 claims description 3
- XCJXQCUJXDUNDN-UHFFFAOYSA-N chlordene Chemical group C12C=CCC2C2(Cl)C(Cl)=C(Cl)C1(Cl)C2(Cl)Cl XCJXQCUJXDUNDN-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 101001031591 Mus musculus Heart- and neural crest derivatives-expressed protein 2 Proteins 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 150000002825 nitriles Chemical class 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 20
- 239000004327 boric acid Substances 0.000 abstract description 5
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 20
- 238000001228 spectrum Methods 0.000 description 20
- 239000004814 polyurethane Substances 0.000 description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 16
- 229920002635 polyurethane Polymers 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 238000002485 combustion reaction Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 235000011121 sodium hydroxide Nutrition 0.000 description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 239000002861 polymer material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 6
- 239000003610 charcoal Substances 0.000 description 6
- 235000019504 cigarettes Nutrition 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 231100000419 toxicity Toxicity 0.000 description 6
- 230000001988 toxicity Effects 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 239000004809 Teflon Substances 0.000 description 5
- 229920006362 Teflon® Polymers 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229960002645 boric acid Drugs 0.000 description 4
- 235000010338 boric acid Nutrition 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 231100000252 nontoxic Toxicity 0.000 description 4
- 230000003000 nontoxic effect Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 230000001629 suppression Effects 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 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
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 2
- 150000003921 pyrrolotriazines Chemical class 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- SUPXSFXAMJPEPH-UHFFFAOYSA-N 5h-pyrrolo[3,2-d]triazine Chemical class N1=NC=C2NC=CC2=N1 SUPXSFXAMJPEPH-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 description 1
- 208000032825 Ring chromosome 2 syndrome Diseases 0.000 description 1
- DBQBWZSDXNFYJI-UHFFFAOYSA-N [B].[N].[P] Chemical compound [B].[N].[P] DBQBWZSDXNFYJI-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 1
- BRTALTYTFFNPAC-UHFFFAOYSA-N boroxin Chemical group B1OBOBO1 BRTALTYTFFNPAC-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical group CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- C07F9/659—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 having three phosphorus atoms as ring hetero atoms in the same ring
-
- 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
- C08K5/55—Boron-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses star-like boron phosphazene derivative expansion type flame retardant and preparation method thereof.The star-like boron phosphazene derivative of the present invention is six (4 boric acid phenoxy group) ring phosphonitriles.During preparation, in the anhydrous tetrahydrofuran solution that first hexachlorocyclotriph,sphazene is added to, stir under nitrogen atmosphere, in the anhydrous tetrahydrofuran solution for being added drop-wise to p bromophenol and sodium hydroxide, flow back, filter in a nitrogen atmosphere, tetrahydrofuran is evaporated off, rinse, separated with silica gel chromatographic column, obtain intermediate product 1；Intermediate product 1 is dissolved in the THF newly steamed, triisopropyl borate ester is added, the addition butyl lithium under 70 DEG C of 78 DEG C of nitrogen atmospheres dropwise reacts 1 2h, is then gradually heating to room temperature, reaction overnight；Filtering, is evaporated off THF, obtains intermediate product 2；Flushing liquor is separated with chromatographic column, obtains target product.Invention products therefrom can be as excellent organic fire-retardant.
Description
Technical field
The present invention relates to the field of fire-proof technology of high-molecular organic material, and in particular to star-like boron phosphazene derivative intumescent
Fire retardant and preparation method thereof.
Background technology
High polymer material species is various, and with many excellent performances so that high polymer material is in national economy and people
The people's livelihood is obtained a wide range of applications in living.But most high polymer material has inflammability, the burning meeting of high polymer material
The serious property and life security for threatening people, which prevent high polymer material some fields further development, fire retardant
Development can be very good to reduce such harm.
Fire retardant can be divided into inorganic combustion inhibitor and organic fire-retardant by attribute, and inorganic combustion inhibitor has low cigarette, low toxicity, nothing
Halogen, stability is good, it is cheap the advantages of, but there is also addition it is big, with material compatibility is poor, can reduce material property etc. scarce
Point.Organic fire-retardant species is various.Widely used at present is traditional organophosphor system and organic halogenated flame retardant, and they have good
Good fire resistance, but itself exist toxic gas etc. can be produced in toxicity and processing and combustion process.For example, organic halogen
Fire retardant can discharge toxic and corrosive hydrogen halide etc., be also easy to produce secondary in the processing and combustion process of material
Pollution, is impacted to environment；Organophosphorous fire retardant itself has larger toxicity, also with larger stink.So synthesis
Toxicity is low, and the new organic fire-retardant of excellent fireproof performance is imperative.With the continuous appearance of the new environmental regulation of various countries, tool
Have nontoxic or low toxicity, suppression cigarette or low smoke performance new green environment protection organic fire-retardant be 21 century organic fire-retardant development must
Right trend.
Chinese invention patent application 201610586811.3 discloses the expansion type flame retardant based on star-like pyrrolotriazine derivatives
And preparation method thereof.The entitled 2,4,6- tri- based on the star-like pyrrolotriazine derivatives-{ 2- (ring -2- oxygen of [1,3,2] dioxy boron penta
Generation)-ethyoxyl } -1,3,5-triazines, as expansion type flame retardant；During preparation, toluene and ethylene glycol are mixed, and be warming up to 40-
60 DEG C, boric acid is added, heating, stirring to boric acid is completely dissolved；It is stirred at reflux to water knockout drum moisture not to be further added by, keeps the temperature
Degree continues to react 2-5h；Reaction solution vacuum distillation is removed into toluene, vacuum drying obtains intermediate product；Intermediate product is dissolved in four
In hydrogen tetrahydrofuran solution；Under nitrogen protection, Cyanuric Chloride is dissolved in tetrahydrofuran solution, then adds sodium hydroxide；By several times
The tetrahydrofuran solution dissolved with intermediate product is added, purification obtains star-like pyrrolotriazine derivatives.Product obtained by the invention can be done
For excellent environment-friendly type organic fire-retardant.But the molecule of the expansion type flame retardant proposed in prior art 201610586811.3
Contain borate group in structure, its anti-flammability of the compound containing borate functional group is compared with the compound of boracic acid functional group
Anti-flammability is low.In addition, comprising only boron, nitrogen in the molecular structure of expansion type flame retardant proposed in technology 201610586811.3
Two kinds of ignition-proof elements, its flame retardant effect is needed to be further improved.
The content of the invention
It is an object of the invention to overcome the shortcoming of prior art there is provided there is not facile hydrolysis under a kind of normal temperature, stability is high,
Good flame retardation effect, the small star-like boron phosphazene derivative expansion type flame retardant of small toxicity, smoke amount and preparation method thereof.
Boron element, P elements and nitrogen all belong to ignition-proof element, although the organophosphorous fire retardant containing phosphorus in molecular structure
With good fire resistance, but it has certain toxicity.And only contain a kind of having for ignition-proof element nitrogen in organic molecular structure
Machine nitrogen combustion inhibitor is although nontoxic, but its fire resistance is relatively weak.The organoboron flame-retardant of ignition-proof element boron is comprised only, it hinders
Fire performance still not high enough.If containing boron, nitrogen, phosphorus ignition-proof element in the molecular structure of fire retardant simultaneously, then the fire retardant
It is possible on the one hand combine the respective fire resistance of ignition-proof element, the fire resistance of organic nitrogen is on the other hand improved again.
Boron flame retardant is the fire retardant of a class non-toxic efficient, can be effectively promoted high polymer material into charcoal, suppress combustion
Burn；The fire retardant mechanism of phosphorus flame retardant is mainly to form barrier film to reach flame retardant effect, and the thermal degradation products of fire retardant promote
Polymer surfaces rapid dehydration and carbonize, and then formed charring layer.Due to simple substance carbon without produce flame combustion by evaporation and
Decomposition combustion, therefore, with fire-resisting protection effect, it can also decompose the nonvolatile glassy mass of generation under ignition temperature,
It is coated on the surface of polymer, and this fine and close protective layer plays separation layer；And expansion type flame retardant is generally efficiently
Nontoxic fire retardant, material is in burning, and the uniform porous carbonaceous froth bed of one layer of Surface Creation can play heat-insulated, oxygen barrier, suppression
The effect of cigarette, anti-molten drop.
The present invention combines expanding fire retardant and boron, the characteristic of phosphorus flame retardant, invents new organic boron-nitrogen-phosphorus fire retardant.
Boron, nitrogen two are comprised only in the molecular structure of expansion type flame retardant proposed in prior art 201610586811.3
Ignition-proof element is planted, its intermolecular cooperative flame retardant effect is not as good as the collaboration resistance containing boron, nitrogen, three kinds of ignition-proof elements of phosphorus in the present invention
Fuel efficiency fruit.
The object of the invention is achieved through the following technical solutions：
Star-like boron phosphazene derivative expansion type flame retardant, entitled six (4- boric acid-phenoxy group)-ring phosphonitrile (HBPCP), tool
There is following molecular structure：
The preparation method of the star-like boron phosphazene derivative expansion type flame retardant, including the steps：
The first step：In the anhydrous tetrahydrofuran solution that hexachlorocyclotriph,sphazene is added to, stir, be added dropwise under nitrogen atmosphere
Into the anhydrous tetrahydrofuran solution of p bromophenol and sodium hydroxide, flow back 12h-24h in a nitrogen atmosphere；The chlordene ring three
The mol ratio of phosphonitrile, p bromophenol and sodium hydroxide is 1:6-9:8-10；
Second step：After reaction terminates, filtering is evaporated off tetrahydrofuran, punching is used as using the mixed liquor of dichloromethane and petroleum ether
Washing lotion, is separated with silica gel chromatographic column, obtains intermediate product 1；
3rd step：Intermediate product 1 is dissolved in the THF newly steamed, triisopropyl borate ester is added, at -70 DEG C -- 78 DEG C of nitrogen
Addition butyl lithium under atmosphere dropwise, reacts 1-2h, is then gradually heating to room temperature, reaction overnight；Filtering, is evaporated off THF, in obtaining
Between product 2；Then with 1.5-3M watery hydrochloric acid hydrolysis 2-4h, there is solid precipitation, suction filtration removes solution；
4th step：Using the mixed liquor of dichloromethane and ethyl acetate as flushing liquor, separated with chromatographic column, obtain mesh
Mark the star-like boron phosphazene derivative expansion type flame retardant of product.
Further to realize the object of the invention, it is preferable that anhydrous tetrahydro furan of the first step per 100mL adds 0.015-
0.02mol hexachlorocyclotriph,sphazenes.
Preferably, the first step per 100-200mL anhydrous tetrahydro furan in add 0.045-0.18mol p bromophenols and
0.06-0.2mol sodium hydroxides.
Preferably, the volume ratio of dichloromethane and petroleum ether is 1 in second step:1-2.
Preferably, the THF newly steamed per 100-150mL in the 3rd step adds 8-12g intermediate products 1, and 10-15g boric acid three is different
Propyl ester and 16-24mL butyl lithiums.
Preferably, the concentration range of watery hydrochloric acid is 1.5M-3M in the 3rd step, is used per the corresponding watery hydrochloric acid of 1g intermediate products 2
Measure as 50-100ml.
Preferably, the volume ratio of dichloromethane and ethyl acetate is 1 in the 4th step:1-5.
The present invention has the following advantages that and beneficial effect compared with prior art：
1) containing borate group in the expansion type flame retardant proposed in 201610586811.3, its molecular structure,
There are facile hydrolysis, the not high shortcoming of stability at normal temperatures.Star-like boron phosphazene derivative expansion type flame retardant provided by the present invention,
Contain boric acid base group, phosphazene backbone and phenoxy group in its molecular structure, improve its stability at room temperature.
2) present invention is dehydrated and discharges fire retardant gas in combustion, and moisture evaporation can absorb heat, reduces base material
Surface temperature, fire retardant gas can dilute combustible concentration, promote high polymer material to form the layer of charcoal of stable expansion, be covered in
The surface of base material, serves the effect of thermal insulation layer, and the exchange of isolation heat and oxygen prevents the burning of combustible；
3) star-like boron phosphazene derivative expansion type flame retardant provided by the present invention can also catch high polymer decomposable process
The living radical of middle generation, suppresses chain reaction.Therefore this star-like expansion type flame retardant is expected to turn into excellent environment-friendly type
Organic fire-retardant.
4) present invention is it is also possible to the toxicity for solving existing fire retardant presence is big, smoke amount is big, easily drippage, heat endurance is poor
The shortcomings of.
Embodiment
To more fully understand the present invention, with reference to embodiment, the present invention is described further, but the reality of the present invention
Mode is applied not limit so.
Embodiment 1：The preparation of star-like boron phosphazene derivative expansion type flame retardant (HBPCP)
The first step：5.33g hexachlorocyclotriph,sphazenes are added in 50mL anhydrous tetrahydrofuran solution.Under nitrogen atmosphere
Stirring, while above-mentioned tetrahydrofuran solution to be added drop-wise to the 100mL anhydrous four of 18.34g p bromophenols and 7g sodium hydroxides dropwise
In hydrogen tetrahydrofuran solution；Flow back 12h in a nitrogen atmosphere；
Second step：After reaction terminates, tetrahydrofuran is evaporated off, using volume ratio as 1 in filtering:2 dichloromethane and petroleum ether
Mixed liquor is separated as flushing liquor with silica gel chromatographic column, obtains intermediate product 1；
3rd step：10g intermediate products 1 are dissolved in the THF that 100mL newly steams, 12g triisopropyl borate esters are added, at -78 DEG C
Addition 20mL butyl lithiums under nitrogen atmosphere dropwise, react 2h, are then gradually heating to room temperature, reaction overnight.Filtering, is evaporated off
THF, obtains intermediate product 2, then with 1.5M watery hydrochloric acid hydrolysis 2h, there is solid precipitation, suction filtration removes solution；
4th step：Using volume ratio as 1:5 dichloromethane and the mixed liquor of ethyl acetate are entered as flushing liquor with chromatographic column
Row separation, obtains target product HBPCP.
Resulting product is levied using proton nmr spectra and carbon stave, structural characterization data are as follows：
1H-NMR(600MHz,DMSO-d6,ppm):δ6.70(t,12H),7.10(t,12H)
Wherein δ=6.70 and 7.10ppm are the peak on phenyl ring.
13C-NMR(150MHz,DMSO-d6,ppm):δ121.1(t,6C),130.5(t,12C),116.9(t,12C),
157.3(t,6C)
Understand that the product is HBPCP with reference to hydrogen spectrum carbon spectrum.
Used instrument:Hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, place of production Germany
Bruker companies；Carbon spectrum (13C NMR) nuclear magnetic resonance spectrometer, specification AVANCE-600, place of production Bruker companies of Germany.
Embodiment 2：The preparation of star-like boron phosphazene derivative expansion type flame retardant (HBPCP)
The first step：6.95g hexachlorocyclotriph,sphazenes are added in 75mL anhydrous tetrahydrofuran solution.Under nitrogen atmosphere
Stirring, while above-mentioned tetrahydrofuran solution to be added drop-wise to the 125mL anhydrous four of 24.2g p bromophenols and 7.9g sodium hydroxides dropwise
In hydrogen tetrahydrofuran solution；Flow back 14h in a nitrogen atmosphere；
Second step：After reaction terminates, tetrahydrofuran is evaporated off, using volume ratio as 1 in filtering:3 dichloromethane and petroleum ether
Mixed liquor is separated as flushing liquor with silica gel chromatographic column, obtains intermediate product 1；
3rd step：12g intermediate products 1 are dissolved in the THF that 100mL newly steams, 13g triisopropyl borate esters are added, at -78 DEG C
Addition 25mL butyl lithiums under nitrogen atmosphere dropwise, react 3h, are then gradually heating to room temperature, reaction overnight.Filtering, is evaporated off
THF, obtains intermediate product 2, then with 2M watery hydrochloric acid hydrolysis 3h, there is solid precipitation, suction filtration removes solution；
4th step：Using volume ratio as 1:5 dichloromethane and the mixed liquor of ethyl acetate are entered as flushing liquor with chromatographic column
Row separation, obtains target product HBPCP.
Resulting product is levied using proton nmr spectra and carbon stave, structural characterization data are as follows：
1H-NMR(600MHz,DMSO-d6,ppm):δ6.68(t,12H),7.18(t,12H)
Wherein δ=6.68 and 7.18ppm are the peak on phenyl ring.
13C-NMR(150MHz,DMSO-d6,ppm):δ122.2(t,6C),131.3(t,12C),115.6(t,12C),
158.3(t,6C)
Understand that the product is HBPCP with reference to hydrogen spectrum carbon spectrum.
Used instrument:Hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, place of production Germany
Bruker companies；Carbon spectrum (13C NMR) nuclear magnetic resonance spectrometer, specification AVANCE-600, place of production Bruker companies of Germany.
Embodiment 3：The preparation of star-like boron phosphazene derivative expansion type flame retardant (HBPCP)
The first step：8.71g hexachlorocyclotriph,sphazenes are added in 100mL anhydrous tetrahydrofuran solution.In nitrogen atmosphere
Lower stirring, at the same by above-mentioned tetrahydrofuran solution be added drop-wise to dropwise the 150mL of 34.68g p bromophenols and 9.87g sodium hydroxides without
In water tetrahydrofuran solution；Flow back 16h in a nitrogen atmosphere；
Second step：After reaction terminates, tetrahydrofuran is evaporated off, using volume ratio as 1 in filtering:3 dichloromethane and petroleum ether
Mixed liquor is separated as flushing liquor with silica gel chromatographic column, obtains intermediate product 1；
3rd step：14g intermediate products 1 are dissolved in the THF that 150mL newly steams, 15g triisopropyl borate esters are added, at -78 DEG C
Addition 24mL butyl lithiums under nitrogen atmosphere dropwise, react 4h, are then gradually heating to room temperature, reaction overnight.Filtering, is evaporated off
THF, obtains intermediate product 2, then with 3M watery hydrochloric acid hydrolysis 4h, there is solid precipitation, suction filtration removes solution；
4th step：Using volume ratio as 1:5 dichloromethane and the mixed liquor of ethyl acetate are entered as flushing liquor with chromatographic column
Row separation, obtains target product HBPCP.
Resulting product is levied using proton nmr spectra and carbon stave, structural characterization data are as follows：
1H-NMR(600MHz,DMSO-d6,ppm):δ6.47(t,12H),7.08(t,12H)
Wherein δ=6.47 and 7.08ppm are the peak on phenyl ring.
13C-NMR(150MHz,DMSO-d6,ppm):δ121.7(t,6C),132.1(t,12C),118.9(t,12C),
157.8(t,6C)。
Understand that the product is HBPCP with reference to hydrogen spectrum carbon spectrum.
Used instrument:Hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, place of production Germany
Bruker companies；Carbon spectrum (13C NMR) nuclear magnetic resonance spectrometer, specification AVANCE-600, place of production Bruker companies of Germany.
Embodiment 4：The preparation of star-like boron phosphazene derivative expansion type flame retardant (HBPCP)
The first step：10.43g hexachlorocyclotriph,sphazenes are added in 125mL anhydrous tetrahydrofuran solution.In nitrogen atmosphere
Lower stirring, while above-mentioned tetrahydrofuran solution to be added drop-wise to the 175mL of 44.12g p bromophenols and 11.41g sodium hydroxides dropwise
In anhydrous tetrahydrofuran solution；Flow back 20h in a nitrogen atmosphere；
Second step：After reaction terminates, tetrahydrofuran is evaporated off, using volume ratio as 1 in filtering:3 dichloromethane and petroleum ether
Mixed liquor is separated as flushing liquor with silica gel chromatographic column, obtains intermediate product 1；
3rd step：16g intermediate products 1 are dissolved in the THF that 150mL newly steams, 16g triisopropyl borate esters are added, at -78 DEG C
Addition 25mL butyl lithiums under nitrogen atmosphere dropwise, react 4h, are then gradually heating to room temperature, reaction overnight.Filtering, is evaporated off
THF, obtains intermediate product 2, then with 1.8M watery hydrochloric acid hydrolysis 5h, there is solid precipitation, suction filtration removes solution；
4th step：Using volume ratio as 1:5 dichloromethane and the mixed liquor of ethyl acetate are entered as flushing liquor with chromatographic column
Row separation, obtains target product HBPCP.
Resulting product is levied using proton nmr spectra and carbon stave, structural characterization data are as follows：
1H-NMR(600MHz,DMSO-d6,ppm):δ6.56(t,12H),7.22(t,12H)
Wherein δ=6.56 and 7.22ppm are the peak on phenyl ring.
13C-NMR(150MHz,DMSO-d6,ppm):δ121.4(t,6C),129.1(t,12C),117.2(t,12C),
157.7(t,6C)
Understand that the product is HBPCP with reference to hydrogen spectrum carbon spectrum.
Used instrument:Hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, place of production Germany
Bruker companies；Carbon spectrum (13C NMR) nuclear magnetic resonance spectrometer, specification AVANCE-600, place of production Bruker companies of Germany.
Embodiment 5：The preparation of star-like boron phosphazene derivative expansion type flame retardant (HBPCP)
The first step：12.17g hexachlorocyclotriph,sphazenes are added in 150mL anhydrous tetrahydrofuran solution.In nitrogen atmosphere
Lower stirring, at the same by above-mentioned tetrahydrofuran solution be added drop-wise to dropwise the 200mL of 54.48g p bromophenols and 15.1g sodium hydroxides without
In water tetrahydrofuran solution；Flow back 24h in a nitrogen atmosphere；
Second step：After reaction terminates, tetrahydrofuran is evaporated off, using volume ratio as 1 in filtering:5 dichloromethane and petroleum ether
Mixed liquor is separated as flushing liquor with silica gel chromatographic column, obtains intermediate product 1；
3rd step：18g intermediate products 1 are dissolved in the THF that 200mL newly steams, 20g triisopropyl borate esters are added, at -78 DEG C
Addition 30mL butyl lithiums under nitrogen atmosphere dropwise, react 3-5h, are then gradually heating to room temperature, reaction overnight.Filtering, is evaporated off
THF, obtains intermediate product 2, then with 2.5M watery hydrochloric acid hydrolysis 6h, there is solid precipitation, suction filtration removes solution；
4th step：Using volume ratio as 1:5 dichloromethane and the mixed liquor of ethyl acetate are entered as flushing liquor with chromatographic column
Row separation, obtains target product HBPCP.
Resulting product is levied using proton nmr spectra and carbon stave, structural characterization data are as follows：
1H-NMR(600MHz,DMSO-d6,ppm):δ6.90(t,12H),7.33(t,12H)
Wherein δ=6.90 and 7.33ppm are the peak on phenyl ring.
13C-NMR(150MHz,DMSO-d6,ppm):δ120.1(t,6C),131.7(t,12C),114.9(t,12C),
159.0(t,6C)
Understand that the product is HBPCP with reference to hydrogen spectrum carbon spectrum.
Used instrument:Hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, place of production Germany
Bruker companies；Carbon spectrum (13C NMR) nuclear magnetic resonance spectrometer, specification AVANCE-600, place of production Bruker companies of Germany.
Fire resistance is tested
The relevant assay method of the embodiment of the present invention is as follows.
(1) limited oxygen index (LOI)
According to the standard testings of ASTM D 2863, the batten standard that test is selected is：80mm×10mm×4mm.
(2) vertical burn test (UL-94)
According to the standard testings of ASTM D 3801, the dimensional standard of batten is：125mm×12.7mm×3.2mm.According to sample
Can the burning time of bar, if having a dropping, dropping be ignited the experimental results such as absorbent cotton, and material is set into V-2, V-1, V-
0 three fire-retardant ranks.
Polyurethane (polyurethane, abbreviation PU) is a kind of comprehensive high polymer material of performance, can be used as foamed plastics,
The multiple materials such as coating, rubber, fiber, adhesive and functional polymer.Although PU has more excellent properties, its limit oxygen
Index is relatively low, inflammable, and is easily dripped during burning, makes its application under cover huge hidden danger in industry, life.Recent decades
Come, the fire incident of polyurethane material frequently occurs, and the safety issue of material becomes more and more important.Therefore, the task of top priority,
Improve the anti-flammability of polyurethane, fire safety is improved, as the main trend for expanding its application at this stage.
Application Example 1：
Fire retardant (HBPCP) 0.5g in embodiment 1 is weighed, is added it in 50g polyurethane, is warming up to 100 DEG C and fills
Stirring to fire retardant is divided to be mixed thoroughly.While hot by cast polyurethane into Teflon mould, solidify 3 days at room temperature,
After placing 7 days, its fire resistance is tested.
Application Example 2：
Fire retardant (HBPCP) 2.5g in embodiment 2 is weighed, is added it in 50g polyurethane, is warming up to 100 DEG C and fills
Stirring to fire retardant is divided to be mixed thoroughly.While hot by cast polyurethane into Teflon mould, solidify 3 days at room temperature,
After placing 7 days, its fire resistance is tested.
Application Example 3：
Fire retardant (HBPCP) 5g in embodiment 3 is weighed, is added it in 50g polyurethane, 100 DEG C are warming up to fully
Stirring to fire retardant is mixed thoroughly.While hot by cast polyurethane into Teflon mould, solidify 3 days at room temperature, put
Put after 7 days, test its fire resistance.
Application Example 4：
Fire retardant (HBPCP) 7.5g in embodiment 4 is weighed, is added it in 50g polyurethane, is warming up to 100 DEG C and fills
Stirring to fire retardant is divided to be mixed thoroughly.While hot by cast polyurethane into Teflon mould, solidify 3 days at room temperature,
After placing 7 days, its fire resistance is tested.
Application Example 5：
Fire retardant (HBPCP) 10g in embodiment 5 is weighed, is added it in 50g polyurethane, 100 DEG C are warming up to fully
Stirring to fire retardant is mixed thoroughly.While hot by cast polyurethane into Teflon mould, solidify 3 days at room temperature, put
Put after 7 days, test its fire resistance.
The test data of the flame retardant polyurethane of table 1
As shown in Table 1, with the increase of HBPCP fire retardant mass ratioes, LOI gradually increases.When HBPCP contents are 15%,
UL94V-1 grades are reached.After 20%HBPCP is added, LOI has reached 30.1%, compared with pure PU, improves 12.1%.
UL94V-0 grades are reached simultaneously.When HBPCP content is only 10%, without dripping off, this is mainly due to combustion process
The formation of B-O-C structures, makes layer of charcoal more stablize, while the layer of charcoal formed more expands, can effectively prevent drippage.And combustion
During burning, metaphosphoric acid is formed, polyurethane can be promoted to be dehydrated into charcoal, the layer of charcoal of the stable expansion of formation can effectively completely cut off
Heat, absorption cigarette and absorption combustible granules, so as to reduce HRR, hinder the diffusion of cigarette, reach fire-retardant and suppression cigarette work
With.
After the fire retardant that 20% is added in the present invention, the LOI of polymeric substrate improves 12.1%, and has reached UL94V-
0 grade.Compared with the expansion type flame retardant proposed in 201610586811.3, after the fire retardant for adding 20%, polymer
The LOI of base material improve only 6.3%, and only reach UL94V-1 grades.Because containing boronate in the compounds of this invention
Group, it can form boroxine structure in combustion；And the compounds of this invention contains phosphorus, nitrogen, three kinds of ignition-proof elements of boron,
Cooperative flame retardant effect is more preferable.Based on these two aspects factor, polymeric substrate can be greatly enhanced by adding fire retardant of the present invention
LOI。
Claims (8)
1. star-like boron phosphazene derivative expansion type flame retardant, it is characterised in that (the 4- boric acid-benzene oxygen of the fire retardant entitled six
Base)-ring phosphonitrile (HBPCP), with following molecular structure：
2. the preparation method of star-like boron phosphazene derivative expansion type flame retardant described in claim 1, it is characterised in that including as follows
The step of：
The first step：In the anhydrous tetrahydrofuran solution that hexachlorocyclotriph,sphazene is added to, stir, be added drop-wise to pair under nitrogen atmosphere
In the anhydrous tetrahydrofuran solution of bromophenol and sodium hydroxide, flow back 12h-24h in a nitrogen atmosphere；The phosphorus of chlordene ring three
The mol ratio of nitrile, p bromophenol and sodium hydroxide is 1:6-9:8-10；
Second step：Reaction terminate after, filtering, tetrahydrofuran is evaporated off, the mixed liquor using dichloromethane and petroleum ether as flushing liquor,
Separated with silica gel chromatographic column, obtain intermediate product 1；
3rd step：Intermediate product 1 is dissolved in the THF newly steamed, triisopropyl borate ester is added, at -70 DEG C -- 78 DEG C of nitrogen atmospheres
Under addition butyl lithium dropwise, react 1-2h, be then gradually heating to room temperature, reaction overnight；Filtering, is evaporated off THF, obtains middle production
Thing 2；Then with 1.5-3M watery hydrochloric acid hydrolysis 2-4h, there is solid precipitation, suction filtration removes solution；
4th step：Using the mixed liquor of dichloromethane and ethyl acetate as flushing liquor, separated with chromatographic column, obtain target production
The star-like boron phosphazene derivative expansion type flame retardant of thing.
3. the preparation method of star-like boron phosphazene derivative expansion type flame retardant according to claim 2, it is characterised in that the
Anhydrous tetrahydro furan of one step per 100mL adds 0.015-0.02mol hexachlorocyclotriph,sphazenes.
4. the preparation method of star-like boron phosphazene derivative expansion type flame retardant according to claim 2, it is characterised in that the
One step adds 0.045-0.18mol p bromophenols and 0.06-0.2mol hydroxides in the anhydrous tetrahydro furan per 100-200mL
Sodium.
5. the preparation method of star-like boron phosphazene derivative expansion type flame retardant according to claim 2, it is characterised in that the
The volume ratio of dichloromethane and petroleum ether is 1 in two steps:1-2.
6. the preparation method of star-like boron phosphazene derivative expansion type flame retardant according to claim 2, it is characterised in that the
The THF newly steamed per 100-150mL in three steps adds 8-12g intermediate products 1,10-15g triisopropyl borate esters and 16-24mL butyl
Lithium.
7. the preparation method of star-like boron phosphazene derivative expansion type flame retardant according to claim 2, it is characterised in that the
The concentration range of watery hydrochloric acid is 1.5M-3M in three steps, is 50-100ml per the corresponding watery hydrochloric acid consumption of 1g intermediate products 2.
8. the preparation method of star-like boron phosphazene derivative expansion type flame retardant according to claim 2, it is characterised in that the
The volume ratio of dichloromethane and ethyl acetate is 1 in four steps:1-5.
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