CN105732712B - A kind of phenyl phosphate phosphorus nitrogen synergistic fire retardant of unit containing s-triazine structure, preparation method and applications - Google Patents
A kind of phenyl phosphate phosphorus nitrogen synergistic fire retardant of unit containing s-triazine structure, preparation method and applications Download PDFInfo
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- CN105732712B CN105732712B CN201610149786.2A CN201610149786A CN105732712B CN 105732712 B CN105732712 B CN 105732712B CN 201610149786 A CN201610149786 A CN 201610149786A CN 105732712 B CN105732712 B CN 105732712B
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- phenoxy group
- phenyl phosphate
- triazine
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 56
- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical group C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 title claims abstract description 27
- QYSFHZOEZLZENM-UHFFFAOYSA-N OP(O)(OC1=CC=CC=C1)=O.OP(O)(OC1=CC=CC=C1)=O.OP(O)(OC1=CC=CC=C1)=O.N.P Chemical compound OP(O)(OC1=CC=CC=C1)=O.OP(O)(OC1=CC=CC=C1)=O.OP(O)(OC1=CC=CC=C1)=O.N.P QYSFHZOEZLZENM-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical class CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 20
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 claims abstract description 18
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 12
- 125000003963 dichloro group Chemical group Cl* 0.000 claims abstract description 12
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims abstract description 12
- 239000011230 binding agent Substances 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- -1 phenoxy group phosphoryl chloride phosphorus oxychlorides Chemical class 0.000 claims abstract description 8
- GRWIABMEEKERFV-UHFFFAOYSA-N methanol;oxolane Chemical compound OC.C1CCOC1 GRWIABMEEKERFV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000000843 powder Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N methanol Substances OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 6
- 239000012279 sodium borohydride Substances 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- YAVVGPBYBUYPSR-UHFFFAOYSA-N benzene;oxygen Chemical compound [O].C1=CC=CC=C1 YAVVGPBYBUYPSR-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- GRLQBYQELUWBIO-UHFFFAOYSA-N 4,6-dichlorobenzene-1,3-diol Chemical compound OC1=CC(O)=C(Cl)C=C1Cl GRLQBYQELUWBIO-UHFFFAOYSA-N 0.000 claims description 2
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 2
- 229940113088 dimethylacetamide Drugs 0.000 claims description 2
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims 1
- 230000007935 neutral effect Effects 0.000 claims 1
- 229960001755 resorcinol Drugs 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 239000003610 charcoal Substances 0.000 abstract description 5
- 239000003822 epoxy resin Substances 0.000 abstract description 5
- 229920000647 polyepoxide Polymers 0.000 abstract description 5
- 238000000354 decomposition reaction Methods 0.000 abstract description 3
- 239000007789 gas Substances 0.000 abstract description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 description 16
- 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 description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 230000000979 retarding effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 0 CC(*C1=CC=C(*)CC=C1)N=C(N=C(N)Oc1ccccc1)OC(C=C=C)=C Chemical compound CC(*C1=CC=C(*)CC=C1)N=C(N=C(N)Oc1ccccc1)OC(C=C=C)=C 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 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 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- BZCGWAXQDLXLQM-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O.ClP(Cl)(Cl)=O BZCGWAXQDLXLQM-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 150000003918 triazines Chemical class 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
- C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
- C07F9/6521—Six-membered rings
-
- 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
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
- C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
A kind of preparation method and applications of the phenyl phosphate phosphorus nitrogen synergistic fire retardant of the unit containing s-triazine structure.In the presence of organic mixed solvent methanol tetrahydrofuran, (4 aldehyde radical phenoxy group) 1,3,5 s-triazine of 2,4 two phenoxy group 6 and NaHB4Intermediate I is made in reaction, phenoxy group phosphinylidyne dichloro and resorcin reaction synthetic intermediate II (the double phenoxy group phosphoryl chloride phosphorus oxychlorides of resorcinol), N, N dimethylformamides make solvent, triethylamine makees acid binding agent, and the intermediate I outward appearance three-source integrated with intermediate II reaction spanning set acid source, charcoal source, source of the gas is white powder, the phenyl phosphate phosphorus nitrogen synergistic fire retardant of the unit containing s-triazine structure of excellent flame retardancy.The initial decomposition temperature of the fire retardant is about 331 DEG C, and in 470 DEG C of weightlessness 6%, the carbon yield of 800 DEG C of fire retardants reaches 51%, and the fire retardant has preferable heat endurance, and carbon yield is high, available for epoxy resin, ABS halogen-free flame retardants.
Description
Technical field
The invention belongs to phosphorus nitrogen cooperative resistance combustion compound technical, and in particular to a kind of unit containing s-triazine structure
Phenyl phosphate phosphorus nitrogen synergistic fire retardant, the fire retardant can not only be used for reactive flame retardant and prepare halogen-free flame-retardant resin, but also as
Additive flame retardant is used for the halogen-free flame retardants of engineering plastics.
Background technology
Triazine derivative is the compound that a major class is rich in tertiary carbon structure, has Halogen, low toxicity, decomposition temperature high, right
The physical and mechanical properties of material influence it is small, impervious go out, the advantages that flame retarding efficiency is high.And organic phosphorus compound is thermally decomposed to generate
The oxyacid of phosphorus and its some polymer, this kind of acid can be catalyzed hydroxyl compound heat absorption be dehydrated into charcoal reaction, generation water and
Coke, phosphorus are largely residued in layer of charcoal, and this graphite-like layer of charcoal is fire retardant, heat-insulated, oxygen barrier, burning is suffocated, meanwhile, coke layer
Heat conductivility is poor, reduces the heat of transmission base material, and the thermal decomposition of base material slows down, and organic phosphorus flame retardant is pyrolyzed what is formed
Contain PO free radicals in gaseous products, it can capture H free radicals and OH free radicals, cause H in flame and
OH concentration is greatly reduced, so as to play a part of suppressing burning chain reaction.In order to develop the higher fire retardant of flame retarding efficiency,
The core texture segment of double s-triazine, phenyl phosphate compound rationally assemble and modify, synthesized containing s-triazine structure
The phenyl phosphate phosphorus nitrogen synergistic fire retardant of unit.
The content of the invention
It is an object of the invention to provide a kind of technique is simple, production cost is low, the high preparation of flame retarding efficiency contains s-triazine
The phenyl phosphate phosphorus nitrogen synergistic fire retardant of construction unit.Phenoxy group-the 6- of 2,4- bis- (4- aldehyde radicals phenoxy group) -1,3,5- s-triazine with
NaHB4Intermediate I, phenoxy group phosphinylidyne dichloro and (the double benzene oxygen of resorcinol of resorcin reaction synthetic intermediate II are made in reaction
Base phosphoryl chloride phosphorus oxychloride), finally in the presence of organic solvent, acid binding agent, intermediate I and intermediate II reaction spanning set acid source, charcoal source,
The three-source integrated outward appearance of source of the gas is white powder, the collaboration of the phenyl phosphate phosphorus nitrogen of the unit containing s-triazine structure of excellent flame retardancy
Fire retardant.
The purpose of the present invention is realized in：A kind of phenyl phosphate phosphorus nitrogen synergistic fire retardant of the unit containing s-triazine structure,
The compound has following chemical structural formula：
The preparation method of the phenyl phosphate phosphorus nitrogen synergistic fire retardant of the unit containing s-triazine structure：
A：In methanol-tetrahydrofuran (VMethanol:VTetrahydrofuran=1:1) in the mixed solvent adds phenoxy group -6- (the 4- aldehyde of 2,4- bis-
Phenoxyl) -1,3,5- s-triazine, stirring reaction 20-40min, adds sodium borohydride, is warmed to room temperature follow-up under ice cooling, 4
Continuous stirring reaction 1.5-2.0 hours, concentrated hydrochloric acid adjust reacting liquid pH value to be spin-dried for solvent to 5.5-6.5 and obtain white solid, in being washed to
Property obtains intermediate I, and reaction equation is as follows：
In the step, 2,4- bis- phenoxy group -6- (4- aldehyde radicals phenoxy group) -1, the material of 3,5- s-triazine and sodium borohydride
The ratio between amount is 1:7.0-12, the weight of methanol-tetrahydrofuran mixed solvent are the 7-10 of intermediate I and sodium borohydride gross weight
Times.
B：By in a part of phenoxy group phosphinylidyne dichloro heating response device, after being warming up to 100-150 DEG C, in the case where being stirred continuously,
Phenoxy group phosphinylidyne dichloro, resorcinol is added dropwise into reactor simultaneously, 12-18h is reacted at 100-150 DEG C, reaction is to without chlorine
Change hydrogen to release, be evaporated under reduced pressure, steam the phenoxy group phosphinylidyne dichloro not reacted, obtain the double phenoxy group phosphoryl chloride phosphorus oxychlorides of resorcinol, i.e.,
Intermediate II, reaction equation are as follows：
In the step, resorcinol, the ratio between the amount of material of phenoxy group phosphinylidyne dichloro are 1:5.0-8.0.
C：Intermediate I is added in the reactor for preset organic solvent, acid binding agent is added dropwise under ice cooling, 4, stirring makes
The organic solvent containing intermediate II is added dropwise after dissolving in it, after being added dropwise, is heated to 140-180 DEG C, is steamed after the completion of reaction
Organic solvent, pour into frozen water, recrystallize to obtain white crystalline powder, reaction equation is as follows：
The phenyl phosphate phosphorus nitrogen synergistic fire retardant of the unit containing s-triazine structure；
In the step, the ratio between intermediate II, amount of material of intermediate I are 1:2.0-2.5, during the weight of organic solvent is
5-8 times of mesosome I, intermediate II gross weight.The organic solvent be DMAC N,N' dimethyl acetamide, N,N-dimethylformamide,
Any of dimethyl sulfoxide (DMSO) (more preferably N,N-dimethylformamide)；Described acid binding agent is triethylamine, N, N-
Any of dimethylaniline, pyridine (more preferably triethylamine).
The fire retardant can not only be used for reactive flame retardant and prepare halogen-free flame-retardant resin, be used for but also as additive flame retardant
The halogen-free flame retardants of engineering plastics.The phenyl phosphate phosphorus nitrogen synergistic fire retardant of the unit containing s-triazine structure is as epoxy resin, ABS
Fire retardant.
Beneficial effects of the present invention are as follows：
(1) the phenyl phosphate phosphorus nitrogen synergistic fire retardant of the unit provided by the invention containing s-triazine structure, simple to operate, technique
It is advanced, solvent recoverable；
(2) fire retardant provided by the invention is will to be incorporated into phenyl phosphate molecule, reach containing double s-triazine structure units
The purpose of phosphorus nitrogen cooperative flame retardant, there is higher phosphorus content, nitrogen content, heat resistance and high temperature charring rate, can both be used as response type
Fire retardant, it is linked into the thermosetting resins such as epoxy resin and is used, additive flame retardant can be used as again, for satisfaction pair
The higher ABS of fire retardant heat resistant requirements halogen-free flameproof；
(3) product that synthesizes of the present invention, thermostabilization is good, and fire-retardant rate is high, and purity is up to 99.2%；
Embodiment
The invention will be further described with reference to embodiments, but the scope of protection of present invention is not limited to reality
Apply the scope of example statement.
Embodiment 1：
A kind of preparation method containing s-triazine and spiro-phosphate fire retardant, step are：
Methanol-tetrahydrofuran solution (V is sequentially added in flaskMethanol：VTetrahydrofuran=l:1) 400mL, 2,4- bis- phenoxy groups-
The s-triazine 30.80g (0.08mol) of 6- (4- aldehyde radicals phenoxy group) -1,3,5-, stir 20-40min, add boron hydrogen under ice cooling, 4
Change sodium 30.40g (0.80mol), continue to react 1.5-2.0 hours after being warmed to room temperature, after reaction terminates, concentrated hydrochloric acid adjusts reaction solution pH
Value white precipitate generation, is washed to neutrality, recrystallizing methanol obtains intermediate I, white powdery solids, yield to 5.5-6.5
93.8%.
In the flask equipped with agitator, reflux condensing tube and device for absorbing tail gas, 50.64g (0.24mol) benzene oxygen is added
Base phosphinylidyne dichloro, starts to stir, and 26.4g (0.24mol) resorcinols and 202.56g (0.96mol) phenoxy group phosphinylidyne dichloro add
Enter in constant pressure funnel, be warming up to 105 DEG C and start that resorcinol and phenoxy group phosphinylidyne dichloro is added dropwise, control rate of addition, make mixing
Thing 2h or so is dripped off, and is further heated up to 15h is reacted at a temperature of 125 DEG C, after the completion of reaction, is steamed the phenoxy group not reacted
Phosphinylidyne dichloro, obtain intermediate II, beige newborn thick liquid, yield 93.6%.
In the flask equipped with DMF 150mL, 77.42g (0.20mol) intermediate I is added, in ice bath
Cooling is lower to be added dropwise 11.13g (0.11mo1) triethylamine, and stirring makes it that the N of intermediate II, N- dimethyl methyls be slowly added dropwise after dissolving
Amide solution (dissolves intermediate II 45.90g (0.10mol)) in 80mL DMF, stirring, be added dropwise,
140-180 DEG C is gradually heated up to flowing back, DMF is steamed after the completion of reaction, pours into 300mL frozen water, with N, N-
Dimethylformamide-water mixed solvent recrystallizes to obtain target compound, white solid powder, yield 82.6%.
The chemical equation of prepare compound of the present invention is：
The phenyl phosphate phosphorus nitrogen synergistic fire retardant of the unit produced by the present invention containing s-triazine structure, outward appearance is white powder,
The initial decomposition temperature of the compound is about 331 DEG C, reaches 51% up to the carbon yield of 6%, 800 DEG C of fire retardant in 470 DEG C of weightlessness,
This fire retardant has preferable heat endurance, carbon yield height.High temperature carbon yield is higher, and flame retardant effect is also better, therefore synthesize
Fire retardant has preferable flame retardant effect.
The analysis result of the phenyl phosphate phosphorus nitrogen synergistic fire retardant of the unit produced by the present invention containing s-triazine structure is as follows：
Its outward appearance of compound is white solid, results of IR：FT-IR(KBr),v/cm-1：3006cm-1Near
For phenyl ring C-H stretching vibration peaks, 1271cm-1, 1032cm-1It is P=in the spiro-phosphate fire retardant containing s-triazine structure respectively
O and P-O-C absworption peak；1589cm-1, 1481cm-1For the absworption peak of phenyl ring；Proton nmr spectra analysis result：1H NMR
(DMSO-d6,400MHz):7.75-7.68m,6H,Ar-H),7.62-7.41(m,7H,Ar-H),7.36-7.23(m,6H,Ar-
H),7.12-7.06(m,8H,Ar-H),6.91-6.86(m,8H,Ar-H),6.75-6.63(m,7H,Ar-H),5.28(s,4H,
OCH2)).
Embodiment 2：
Solvent DMF changes DMA, other same examples one into, and its target compound is received
Rate 80.3%.
Solvent changes dimethyl sulfoxide, other same examples one, its target compound yield 75.2% into.
Embodiment 3：
Acid binding agent triethylamine changes DMA, other same examples one, its target compound yield 75.2% into.
Acid binding agent triethylamine changes pyridine, other same examples one, its target compound yield 70.9% into.
Embodiment 4：
The amount of intermediate III is increased into 40.65g (0.105mol), other same examples one, its target compound yield
85.9%.
Embodiment 5：
The amount of intermediate III is increased into 42.58g (0.11mol), other same examples one, its target compound yield
88.3%.
Embodiment 6：
The amount of intermediate III is increased into 44.52g (0.115mol), other same examples one, its target compound yield
91.2%.
Embodiment 7：
The amount of intermediate III is increased into 46.45g (0.12mol), other same examples one, its target compound yield
88.5%.
Embodiment 8：
The amount of intermediate III is increased into 48.39g (0.125mol), other same examples one, its target compound yield
84.1%.
The phenyl phosphate of the unit provided by the invention containing s-triazine structure as epoxy resin, ABS fire retardants application such as
Under：
Batten is made according to insulating laminated sheet combustibility testing standard, carries out pole with JF-3 types oxygen index measurer respectively
Limited oxygen index (LOI) is tested, and FZ-5401 types Vertical combustion instrument carries out the test of UL94 vertical combustions performance, measurement result such as following table
Shown in 1-2.
Flame retardant effect of the fire retardant that the embodiment of the present invention 1 of table 1 obtains to epoxy resin
Flame retardant effect of the fire retardant that the embodiment of the present invention 1 of table 2 obtains to ABS
Claims (4)
1. a kind of phenyl phosphate phosphorus nitrogen synergistic fire retardant of unit containing s-triazine structure, its chemical structural formula are as follows：
2. a kind of preparation method of the phenyl phosphate phosphorus nitrogen synergistic fire retardant of the unit containing s-triazine structure described in claim 1,
It is characterised in that it includes following steps：
A：In methanol-tetrahydrofuran VMethanol:VTetrahydrofuran=1:1 in the mixed solvent adds phenoxy group -6- (the 4- aldehyde radical benzene oxygen of 2,4- bis-
Base) -1,3,5- s-triazine, stirring reaction 20-40min, adds sodium borohydride, continues to stir after being warmed to room temperature under ice cooling, 4
React 1.5-2.0 hours, concentrated hydrochloric acid adjusts reacting liquid pH value to be spin-dried for solvent to 5.5-6.5 and obtain white solid, be washed in neutral obtain
The amount of the material of mesosome I, the described phenoxy group -6- of 2,4- bis- (4- aldehyde radicals phenoxy group) -1,3,5- s-triazine and sodium borohydride it
Than for 1:7.0-12, the weight of methanol-tetrahydrofuran mixed solvent are 7-10 times of intermediate I and sodium borohydride gross weight, instead
Answer equation as follows：
B：A part of phenoxy group phosphinylidyne dichloro is added in reactor, after being warming up to 100-150 DEG C, in the case where being stirred continuously, simultaneously
Phenoxy group phosphinylidyne dichloro, resorcinol is added dropwise into reactor, 12-18h is reacted at 100-150 DEG C, reaction is to without hydrogen chloride
Release, be evaporated under reduced pressure, steam the phenoxy group phosphinylidyne dichloro not reacted, obtain the double phenoxy group phosphoryl chloride phosphorus oxychlorides of resorcinol, i.e., it is middle
Body II, described resorcinol, the ratio between the amount of material of phenoxy group phosphinylidyne dichloro are 1:5.0-8.0 reaction equation is as follows：
C：Intermediate I is added in the reactor for preset organic solvent, acid binding agent is added dropwise under ice cooling, 4, stirring makes its molten
The organic solvent containing intermediate II is added dropwise after solution, after being added dropwise, is heated to 140-180 DEG C, is steamed after the completion of reaction organic
Solvent, pour into frozen water, recrystallize to obtain the ratio between white crystalline powder, described intermediate II, the amount of material of intermediate I as 1:
2.0-2.5, the weight of organic solvent is intermediate I, 5-8 times of intermediate II gross weight, and reaction equation is as follows：
The phenyl phosphate phosphorus nitrogen synergistic fire retardant of the unit containing s-triazine structure.
3. the preparation method of the phenyl phosphate phosphorus nitrogen synergistic fire retardant of the unit according to claim 2 containing s-triazine structure,
It is characterized in that：Organic solvent described in step C is DMAC N,N' dimethyl acetamide, N,N-dimethylformamide, dimethyl sulfoxide (DMSO)
Any of；Described acid binding agent is triethylamine, any of N, accelerine, pyridine.
4. the preparation method of the phenyl phosphate phosphorus nitrogen synergistic fire retardant of the unit according to claim 2 containing s-triazine structure,
It is characterized in that：Organic solvent described in step C is DMF, and described acid binding agent is triethylamine.
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|---|---|---|---|---|
| CN104725665A (en) * | 2015-03-10 | 2015-06-24 | 三峡大学 | Spirocyclic phosphate flame retardant with S-triazine structure as well as preparation method and application of spirocyclic phosphate flame retardant |
| CN104774343A (en) * | 2015-03-10 | 2015-07-15 | 三峡大学 | Phenyl phosphate flame retardant containing DOPO, and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104725665A (en) * | 2015-03-10 | 2015-06-24 | 三峡大学 | Spirocyclic phosphate flame retardant with S-triazine structure as well as preparation method and application of spirocyclic phosphate flame retardant |
| CN104774343A (en) * | 2015-03-10 | 2015-07-15 | 三峡大学 | Phenyl phosphate flame retardant containing DOPO, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
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| Synthesis and characterization of a novel phosphorus–nitrogen‐containingflame retardant and its application for textile;SeChin Chang et al.;《Polym. Adv. Technol.》;20110617;第23卷;第1036-1044页 * |
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