CN106986896B - 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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- CN106986896B CN106986896B CN201710145711.1A CN201710145711A CN106986896B CN 106986896 B CN106986896 B CN 106986896B CN 201710145711 A CN201710145711 A CN 201710145711A CN 106986896 B CN106986896 B CN 106986896B
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- expansion type
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 96
- 229910052796 boron Inorganic materials 0.000 title claims abstract description 35
- -1 boron phosphazene derivative Chemical class 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 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 description 52
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 104
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- 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
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 21
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000011010 flushing procedure Methods 0.000 claims abstract description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 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
- 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
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000003208 petroleum Substances 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 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
- VADKRMSMGWJZCF-UHFFFAOYSA-N 2-bromophenol Chemical compound OC1=CC=CC=C1Br VADKRMSMGWJZCF-UHFFFAOYSA-N 0.000 claims 1
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 229910052744 lithium Inorganic materials 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
- 238000003756 stirring Methods 0.000 abstract description 12
- 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
- 239000000463 material Substances 0.000 description 16
- 229920002635 polyurethane Polymers 0.000 description 16
- 238000005481 NMR spectroscopy Methods 0.000 description 15
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 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
- 238000002485 combustion reaction Methods 0.000 description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 8
- 239000010410 layer Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 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
- 239000000758 substrate Substances 0.000 description 5
- 238000012360 testing method 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
- 239000004327 boric acid Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000000034 method Methods 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
- 150000003921 pyrrolotriazines Chemical class 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
- 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
- 238000002955 isolation Methods 0.000 description 2
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 2
- 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
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 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
- 238000000280 densification 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
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 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
- 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
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- 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 retardants and preparation method thereof.The star-like boron phosphazene derivative of the present invention is six (4- boric acid-phenoxy group)-ring phosphonitriles.When preparation, in the anhydrous tetrahydrofuran solution that first hexachlorocyclotriph,sphazene is added to, it stirs under nitrogen atmosphere, it is added drop-wise in the anhydrous tetrahydrofuran solution of p bromophenol and sodium hydroxide, flows back in a nitrogen atmosphere, filter, tetrahydrofuran is evaporated off, it rinses, is 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, at -70 DEG C -- the addition butyl lithium under 78 DEG C of nitrogen atmospheres dropwise reacts 1-2h, is then gradually heated 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 used 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 technique
High molecular material is many kinds of, and has many excellent performances, so that high molecular material is in national economy and people
It is had been widely used during the people's livelihood is living.However most high molecular material has inflammability, the burning meeting of high molecular material
The property and life security for seriously threatening people, the further development which prevent high molecular material in some fields, fire retardant
Development can be very good to reduce such harm.
Fire retardant can be divided into inorganic fire retardants and organic fire-retardant by attribute, and inorganic fire retardants has low cigarette, low toxicity, nothing
The advantages that halogen, stability are good, cheap, but that there is also additive amounts is big, with that material compatibility is poor, can reduce material property etc. is scarce
Point.Organic fire-retardant is many kinds of.Widely used at present is traditional organic phosphorus and organic halogenated flame retardant, they have good
Good flame retardant property, but itself there are toxicity and processes and can generate toxic gas etc. in 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, impacts environment；Organophosphorous fire retardant itself has biggish toxicity, also has biggish stink.So synthesis
Toxicity is low, and the novel organic fire-retardant of excellent fireproof performance is imperative.With the continuous appearance of the new environmental regulation of various countries, tool
It is non-toxic or low-toxic, 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--{ 2- (penta ring -2- oxygen of [1,3,2] dioxy boron based on star-like pyrrolotriazine derivatives
Generation)-ethyoxyl } -1,3,5-triazines, it is used as expansion type flame retardant；When preparation, toluene and ethylene glycol are mixed, and be warming up to 40-
60 DEG C, boric acid, heating is added, stirring to boric acid is completely dissolved；It is stirred at reflux to moisture in water segregator and is not further added by, keep the temperature
Degree the reaction was continued 2-5h；Reaction solution is evaporated under reduced pressure and removes 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, sodium hydroxide is then added；By several times
The tetrahydrofuran solution dissolved with intermediate product is added, purification obtains star-like pyrrolotriazine derivatives.The obtained product of the invention can be done
For excellent environment-friendly type organic fire-retardant.But the molecule of expansion type flame retardant proposed in the prior art 201610586811.3
Contain borate group in structure, the compound of the compound containing borate functional group its anti-flammability compared with boracic acid functional group
Anti-flammability is low.In addition, containing only boron, nitrogen in the molecular structure of expansion type flame retardant proposed in technology 201610586811.3
Two kinds of ignition-proof elements, flame retardant effect need to be further improved.
Summary of the invention
The purpose of the present invention is to overcome the shortcomings of the existing technology, and providing has not facile hydrolysis under a kind of room temperature, stability is high,
Good flame retardation effect, the small star-like boron phosphazene derivative expansion type flame retardant and preparation method thereof of small toxicity, smoke amount.
Boron element, P elements and nitrogen all belong to ignition-proof element, although containing the organophosphorous fire retardant of phosphorus in molecular structure
With good flame retardant property, 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 flame retardant property is relatively weak.The organoboron flame-retardant of ignition-proof element boron is contained only, is hindered
It is still not high enough to fire performance.If containing boron, nitrogen, phosphorus ignition-proof element, the fire retardant in the molecular structure of fire retardant simultaneously
It is possible that on the one hand combining the respective flame retardant property of ignition-proof element, the flame retardant property of organic nitrogen is on the other hand improved again.
Boron flame retardant is the fire retardant of a kind of non-toxic efficient, can effectively promote high molecular material into charcoal, inhibit combustion
It burns；The fire retardant mechanism of phosphorus flame retardant mainly forms isolation 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 generate flame combustion by evaporation and
Therefore decomposition combustion has fire-resisting protection effect, can also decompose under ignition temperature and generate nonvolatile glassy mass,
It is coated on the surface of polymer, and the protective layer of this densification plays separation layer；And expansion type flame retardant is generally efficient
Nontoxic fire retardant, material is in burning, one layer of Surface Creation uniform porous carbonaceous froth bed, can play heat-insulated, oxygen barrier, suppression
The effect of cigarette, anti-molten drop.
The characteristic of present invention combination expanding fire retardant and boron, phosphorus flame retardant invents novel organic boron-nitrogen-phosphorus fire retardant.
Boron, nitrogen two are contained only in the molecular structure of expansion type flame retardant proposed in the prior art 201610586811.3
Kind ignition-proof element, intermolecular cooperative flame retardant effect is not as good as the collaboration resistance in the present invention containing three kinds of boron, nitrogen, phosphorus ignition-proof elements
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, comprises the following steps that
Step 1: being stirred under nitrogen atmosphere in the anhydrous tetrahydrofuran solution that hexachlorocyclotriph,sphazene is added to, it is added dropwise
To in the anhydrous tetrahydrofuran solution of p bromophenol and sodium hydroxide, flow back 12h-24h in a nitrogen atmosphere；The chlordene ring three
The molar ratio of phosphonitrile, p bromophenol and sodium hydroxide is 1:6-9:8-10；
Step 2: after reaction, tetrahydrofuran is evaporated off in filtering, using the mixed liquor of methylene chloride and petroleum ether as punching
Washing lotion is separated with silica gel chromatographic column, obtains intermediate product 1；
Step 3: 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 heated to room temperature, reaction overnight；Filtering, is evaporated off THF, obtains
Between product 2；Then 2-4h is hydrolyzed with 1.5-3M dilute hydrochloric acid, there is solid precipitation, filtered and remove solution；
Step 4: being separated with chromatographic column using the mixed liquor of methylene chloride and ethyl acetate as flushing liquor, obtaining mesh
Mark the star-like boron phosphazene derivative expansion type flame retardant of product.
To further realize the object of the invention, it is preferable that 0.015- is added in the anhydrous tetrahydro furan of the every 100mL of the first step
0.02mol hexachlorocyclotriph,sphazene.
Preferably, in the anhydrous tetrahydro furan of the every 100-200mL of the first step be added 0.045-0.18mol p bromophenol and
0.06-0.2mol sodium hydroxide.
Preferably, the volume ratio of methylene chloride and petroleum ether is 1:1-2 in second step.
Preferably, 8-12g intermediate product 1 is added in the THF that every 100-150mL newly steams in third step, and 10-15g boric acid three is different
Propyl ester and 16-24mL butyl lithium.
Preferably, the concentration range of dilute hydrochloric acid is 1.5M-3M in third step, and the corresponding dilute hydrochloric acid of every 1g intermediate product 2 is used
Amount is 50-100ml.
Preferably, the volume ratio of methylene chloride and ethyl acetate is 1:1-5 in the 4th step.
The present invention is had the following advantages and beneficial effects: compared with prior art
1) expansion type flame retardant proposed in 201610586811.3, containing borate group in molecular structure,
There are facile hydrolysis, the not high disadvantage of stability at normal temperature.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, improves its stability at room temperature.
2) present invention is dehydrated in combustion and releases fire retardant gas, and moisture evaporation can absorb heat, reduces substrate
Surface temperature, fire retardant gas can dilute combustible concentration, promote high molecular material to form the layer of charcoal for stablizing expansion, are covered on
The surface of substrate, plays the role 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 capture high polymer decomposable process
The living radical of middle generation inhibits chain reaction.Therefore this star-like expansion type flame retardant is expected to become excellent environment-friendly type
Organic fire-retardant.
4) present invention is it is also possible to solve that toxicity existing for existing fire retardant is big, smoke amount is big, easily drippage, thermal stability is poor
The disadvantages of.
Specific embodiment
For a better understanding of the invention, the present invention will be further explained with reference to the examples below, but reality of the invention
It is unlimited so to apply mode.
Embodiment 1: the preparation of star-like boron phosphazene derivative expansion type flame retardant (HBPCP)
Step 1: 5.33g hexachlorocyclotriph,sphazene is added in the anhydrous tetrahydrofuran solution of 50mL.Under nitrogen atmosphere
It stirs, while above-mentioned tetrahydrofuran solution being added drop-wise to the 100mL anhydrous four of 18.34g p bromophenol and 7g sodium hydroxide dropwise
In hydrogen tetrahydrofuran solution；Flow back 12h in a nitrogen atmosphere；
Step 2: after reaction, tetrahydrofuran is evaporated off in filtering, is the methylene chloride and petroleum ether of 1:2 with volume ratio
Mixed liquor is separated as flushing liquor with silica gel chromatographic column, and intermediate product 1 is obtained；
Step 3: 10g intermediate product 1 is dissolved in the THF that 100mL newly steams, 12g triisopropyl borate ester is added, at -78 DEG C
Addition 20mL butyl lithium under nitrogen atmosphere dropwise reacts 2h, is then gradually heated to room temperature, reaction overnight.Filtering, is evaporated off
THF obtains intermediate product 2, then hydrolyzes 2h with 1.5M dilute hydrochloric acid, there is solid precipitation, filters and removes solution；
Step 4: using volume ratio be the methylene chloride of 1:5 and the mixed liquor of ethyl acetate as flushing liquor, with chromatographic column into
Row separation, obtains target product HBPCP.
Obtained product is levied using nuclear magnetic resonance spectroscopy 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)
The product in conjunction with known to hydrogen spectrum carbon spectrum is HBPCP.
Used instrument: hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, place of production Germany
Bruker company；Carbon spectrum (13C NMR) nuclear magnetic resonance spectrometer, specification AVANCE-600, Bruker company, place of production Germany.
Embodiment 2: the preparation of star-like boron phosphazene derivative expansion type flame retardant (HBPCP)
Step 1: 6.95g hexachlorocyclotriph,sphazene is added in the anhydrous tetrahydrofuran solution of 75mL.Under nitrogen atmosphere
It stirs, while above-mentioned tetrahydrofuran solution being added drop-wise to the 125mL anhydrous four of 24.2g p bromophenol and 7.9g sodium hydroxide dropwise
In hydrogen tetrahydrofuran solution；Flow back 14h in a nitrogen atmosphere；
Step 2: after reaction, tetrahydrofuran is evaporated off in filtering, is the methylene chloride and petroleum ether of 1:3 with volume ratio
Mixed liquor is separated as flushing liquor with silica gel chromatographic column, and intermediate product 1 is obtained；
Step 3: 12g intermediate product 1 is dissolved in the THF that 100mL newly steams, 13g triisopropyl borate ester is added, at -78 DEG C
Addition 25mL butyl lithium under nitrogen atmosphere dropwise reacts 3h, is then gradually heated to room temperature, reaction overnight.Filtering, is evaporated off
THF obtains intermediate product 2, then hydrolyzes 3h with 2M dilute hydrochloric acid, there is solid precipitation, filters and removes solution；
Step 4: using volume ratio be the methylene chloride of 1:5 and the mixed liquor of ethyl acetate as flushing liquor, with chromatographic column into
Row separation, obtains target product HBPCP.
Obtained product is levied using nuclear magnetic resonance spectroscopy 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)
The product in conjunction with known to hydrogen spectrum carbon spectrum is HBPCP.
Used instrument: hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, place of production Germany
Bruker company；Carbon spectrum (13C NMR) nuclear magnetic resonance spectrometer, specification AVANCE-600, Bruker company, place of production Germany.
Embodiment 3: the preparation of star-like boron phosphazene derivative expansion type flame retardant (HBPCP)
Step 1: 8.71g hexachlorocyclotriph,sphazene is added in the anhydrous tetrahydrofuran solution of 100mL.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 bromophenol and 9.87g sodium hydroxide without
In water tetrahydrofuran solution；Flow back 16h in a nitrogen atmosphere；
Step 2: after reaction, tetrahydrofuran is evaporated off in filtering, is the methylene chloride and petroleum ether of 1:3 with volume ratio
Mixed liquor is separated as flushing liquor with silica gel chromatographic column, and intermediate product 1 is obtained；
Step 3: 14g intermediate product 1 is dissolved in the THF that 150mL newly steams, 15g triisopropyl borate ester is added, at -78 DEG C
Addition 24mL butyl lithium under nitrogen atmosphere dropwise reacts 4h, is then gradually heated to room temperature, reaction overnight.Filtering, is evaporated off
THF obtains intermediate product 2, then hydrolyzes 4h with 3M dilute hydrochloric acid, there is solid precipitation, filters and removes solution；
Step 4: using volume ratio be the methylene chloride of 1:5 and the mixed liquor of ethyl acetate as flushing liquor, with chromatographic column into
Row separation, obtains target product HBPCP.
Obtained product is levied using nuclear magnetic resonance spectroscopy 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)。
The product in conjunction with known to hydrogen spectrum carbon spectrum is HBPCP.
Used instrument: hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, place of production Germany
Bruker company；Carbon spectrum (13C NMR) nuclear magnetic resonance spectrometer, specification AVANCE-600, Bruker company, place of production Germany.
Embodiment 4: the preparation of star-like boron phosphazene derivative expansion type flame retardant (HBPCP)
Step 1: 10.43g hexachlorocyclotriph,sphazene is added in the anhydrous tetrahydrofuran solution of 125mL.In nitrogen atmosphere
Lower stirring, while above-mentioned tetrahydrofuran solution being added drop-wise to the 175mL of 44.12g p bromophenol and 11.41g sodium hydroxide dropwise
In anhydrous tetrahydrofuran solution；Flow back 20h in a nitrogen atmosphere；
Step 2: after reaction, tetrahydrofuran is evaporated off in filtering, is the methylene chloride and petroleum ether of 1:3 with volume ratio
Mixed liquor is separated as flushing liquor with silica gel chromatographic column, and intermediate product 1 is obtained；
Step 3: 16g intermediate product 1 is dissolved in the THF that 150mL newly steams, 16g triisopropyl borate ester is added, at -78 DEG C
Addition 25mL butyl lithium under nitrogen atmosphere dropwise reacts 4h, is then gradually heated to room temperature, reaction overnight.Filtering, is evaporated off
THF obtains intermediate product 2, then hydrolyzes 5h with 1.8M dilute hydrochloric acid, there is solid precipitation, filters and removes solution；
Step 4: using volume ratio be the methylene chloride of 1:5 and the mixed liquor of ethyl acetate as flushing liquor, with chromatographic column into
Row separation, obtains target product HBPCP.
Obtained product is levied using nuclear magnetic resonance spectroscopy 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)
The product in conjunction with known to hydrogen spectrum carbon spectrum is HBPCP.
Used instrument: hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, place of production Germany
Bruker company；Carbon spectrum (13C NMR) nuclear magnetic resonance spectrometer, specification AVANCE-600, Bruker company, place of production Germany.
Embodiment 5: the preparation of star-like boron phosphazene derivative expansion type flame retardant (HBPCP)
Step 1: 12.17g hexachlorocyclotriph,sphazene is added in the anhydrous tetrahydrofuran solution of 150mL.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 bromophenol and 15.1g sodium hydroxide without
In water tetrahydrofuran solution；It flows back in a nitrogen atmosphere for 24 hours；
Step 2: after reaction, tetrahydrofuran is evaporated off in filtering, is the methylene chloride and petroleum ether of 1:5 with volume ratio
Mixed liquor is separated as flushing liquor with silica gel chromatographic column, and intermediate product 1 is obtained；
Step 3: 18g intermediate product 1 is dissolved in the THF that 200mL newly steams, 20g triisopropyl borate ester is added, at -78 DEG C
Addition 30mL butyl lithium under nitrogen atmosphere dropwise reacts 3-5h, is then gradually heated to room temperature, reaction overnight.Filtering, is evaporated off
THF obtains intermediate product 2, then hydrolyzes 6h with 2.5M dilute hydrochloric acid, there is solid precipitation, filters and removes solution；
Step 4: using volume ratio be the methylene chloride of 1:5 and the mixed liquor of ethyl acetate as flushing liquor, with chromatographic column into
Row separation, obtains target product HBPCP.
Obtained product is levied using nuclear magnetic resonance spectroscopy 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)
The product in conjunction with known to hydrogen spectrum carbon spectrum is HBPCP.
Used instrument: hydrogen spectrum (1H NMR) nuclear magnetic resonance spectrometer, specification AVANCE III HD400, place of production Germany
Bruker company；Carbon spectrum (13C NMR) nuclear magnetic resonance spectrometer, specification AVANCE-600, Bruker company, place of production Germany.
Flame retardant property test
The related measuring method of the embodiment of the present invention is as follows.
(1) limit oxygen index (LOI)
According to 2863 standard testing of ASTM D, the batten standard of selection is tested are as follows: 80mm × 10mm × 4mm.
(2) vertical burn test (UL-94)
According to 3801 standard testing of ASTM D, the dimensional standard of batten are as follows: 125mm × 12.7mm × 3.2mm.According to sample
The burning time of item, if having a dropping, can dropping ignite the experimental results such as absorbent cotton, and material is set to V-2, V-1, V-
0 three fire-retardant ranks.
Polyurethane (polyurethane, abbreviation PU) is a kind of comprehensive high molecular 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 lower, inflammable, and while burning is easy drippage, 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, improves fire safety, become the main trend for expanding its application range 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 flame retardant property 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 flame retardant property is tested.
Application Example 3:
Fire retardant (HBPCP) 5g in embodiment 3 is weighed, is added it in 50g polyurethane, is warming up to 100 DEG C sufficiently
Stirring to fire retardant is mixed thoroughly.While hot by cast polyurethane into Teflon mould, solidifies 3 days at room temperature, put
After setting 7 days, its flame retardant property is tested.
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 flame retardant property is tested.
Application Example 5:
Fire retardant (HBPCP) 10g in embodiment 5 is weighed, is added it in 50g polyurethane, is warming up to 100 DEG C sufficiently
Stirring to fire retardant is mixed thoroughly.While hot by cast polyurethane into Teflon mould, solidifies 3 days at room temperature, put
After setting 7 days, its flame retardant property is tested.
The test data of 1 flame retardant polyurethane of table
As shown in Table 1, with the increase of HBPCP fire retardant mass ratio, LOI is gradually increased.When HBPCP content is 15%,
UL94V-1 grade is reached.After 20%HBPCP is added, LOI has reached 30.1%, compared with pure PU, improves 12.1%.
UL94V-0 grade is reached simultaneously.When the content of HBPCP is only 10%, without dripping off, this is mainly due to combustion process
The formation of B-O-C structure keeps layer of charcoal more stable, and the layer of charcoal being formed simultaneously more expands, and can effectively prevent from dripping.And it fires
During burning, metaphosphoric acid is formed, polyurethane can be promoted to be dehydrated into charcoal, the layer of charcoal for stablizing expansion of formation can effectively completely cut off
Heat, absorption cigarette and absorption combustible granules hinder the diffusion of cigarette to reduce heat release rate, reach fire-retardant and suppression cigarette work
With.
After 20% fire retardant 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 20% fire retardant is added, polymer
The LOI of substrate improves only 6.3%, and only reaches UL94V-1 grade.This is because containing boronate in the compounds of this invention
Group, can form boroxine structure in combustion；And the compounds of this invention contains three kinds of phosphorus, nitrogen, boron ignition-proof elements,
Cooperative flame retardant effect is more preferable.Based on these two aspects factor, fire retardant of the present invention, which is added, can greatly improve polymeric substrate
LOI。
Claims (8)
1. star-like boron phosphazene derivative expansion type flame retardant, which is characterized in that (the 4- boric acid-benzene oxygen of the fire retardant entitled six
Base)-ring phosphonitrile (HBPCP), there is 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:
Step 1: stirred under nitrogen atmosphere in the anhydrous tetrahydrofuran solution that hexachlorocyclotriph,sphazene is added to, it is added drop-wise to pair
In the anhydrous tetrahydrofuran solution of bromophenol and sodium hydroxide, flow back 12h-24h in a nitrogen atmosphere；Three phosphorus of chlordene ring
The molar ratio of nitrile, p bromophenol and sodium hydroxide is 1:6-9:8-10；
Step 2: after reaction, tetrahydrofuran is evaporated off in filtering, using the mixed liquor of methylene chloride and petroleum ether as flushing liquor,
It is separated with silica gel chromatographic column, obtains intermediate product 1；
Step 3: 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 heated to room temperature, reaction overnight；Filtering, is evaporated off THF, obtains intermediate production
Object 2；Then 2-4h is hydrolyzed with 1.5-3M dilute hydrochloric acid, there is solid precipitation, filtered and remove solution；
Step 4: being separated using the mixed liquor of methylene chloride and ethyl acetate as flushing liquor with chromatographic column, target production is obtained
The star-like boron phosphazene derivative expansion type flame retardant of object.
3. the preparation method of star-like boron phosphazene derivative expansion type flame retardant according to claim 2, which is characterized in that the
0.015-0.02mol hexachlorocyclotriph,sphazene is added in the anhydrous tetrahydro furan of the every 100mL of one step.
4. the preparation method of star-like boron phosphazene derivative expansion type flame retardant according to claim 2, which is characterized in that the
0.045-0.18mol p bromophenol and 0.06-0.2mol hydroxide are added in the anhydrous tetrahydro furan of the every 100-200mL of one step
Sodium.
5. the preparation method of star-like boron phosphazene derivative expansion type flame retardant according to claim 2, which is characterized in that the
The volume ratio of methylene chloride and petroleum ether is 1:1-2 in two steps.
6. the preparation method of star-like boron phosphazene derivative expansion type flame retardant according to claim 2, which is characterized in that the
8-12g intermediate product 1,10-15g triisopropyl borate ester and 16-24mL butyl is added in the THF that every 100-150mL newly steams in three steps
Lithium.
7. the preparation method of star-like boron phosphazene derivative expansion type flame retardant according to claim 2, which is characterized in that the
The concentration range of dilute hydrochloric acid is 1.5M-3M in three steps, and the corresponding dilute hydrochloric acid dosage of every 1g intermediate product 2 is 50-100ml.
8. the preparation method of star-like boron phosphazene derivative expansion type flame retardant according to claim 2, which is characterized in that the
The volume ratio of methylene chloride and ethyl acetate is 1:1-5 in four steps.
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