CN108586803A - A kind of spiro-phosphate fire retardant preparation method and applications containing DOPO and benzoxazine - Google Patents
A kind of spiro-phosphate fire retardant preparation method and applications containing DOPO and benzoxazine Download PDFInfo
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- CN108586803A CN108586803A CN201810301027.2A CN201810301027A CN108586803A CN 108586803 A CN108586803 A CN 108586803A CN 201810301027 A CN201810301027 A CN 201810301027A CN 108586803 A CN108586803 A CN 108586803A
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- Prior art keywords
- spiro
- benzoxazine
- fire retardant
- dopo
- phosphate
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 58
- DWSWCPPGLRSPIT-UHFFFAOYSA-N benzo[c][2,1]benzoxaphosphinin-6-ium 6-oxide Chemical compound C1=CC=C2[P+](=O)OC3=CC=CC=C3C2=C1 DWSWCPPGLRSPIT-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 34
- 239000010452 phosphate Substances 0.000 title claims abstract description 34
- CMLFRMDBDNHMRA-UHFFFAOYSA-N 2h-1,2-benzoxazine Chemical compound C1=CC=C2C=CNOC2=C1 CMLFRMDBDNHMRA-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 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 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 polypropylene Polymers 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 8
- 239000004743 Polypropylene Substances 0.000 claims abstract description 7
- 229920001155 polypropylene Polymers 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 claims description 16
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000003960 organic solvent Substances 0.000 claims description 15
- 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 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 6
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 6
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000000654 additive Substances 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 238000010189 synthetic method Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052799 carbon Inorganic materials 0.000 abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 abstract 1
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical class OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 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
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GRZJZRHVJAXMRR-UHFFFAOYSA-N 1-cyclohexyl-2-phenylbenzene Chemical group C1CCCCC1C1=CC=CC=C1C1=CC=CC=C1 GRZJZRHVJAXMRR-UHFFFAOYSA-N 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- SCXYUXXKILZZEC-VFJSDWPHSA-N C/C=C\C(C(CN(COC1)c(cc2)ccc2O)P2(OC3=CC=CC=CC3c3c2cccc3)=O)=C1C(C)=C Chemical compound C/C=C\C(C(CN(COC1)c(cc2)ccc2O)P2(OC3=CC=CC=CC3c3c2cccc3)=O)=C1C(C)=C SCXYUXXKILZZEC-VFJSDWPHSA-N 0.000 description 1
- 0 CC1=C(C=CC=C)c(cccc2)c2OP1=* Chemical compound CC1=C(C=CC=C)c(cccc2)c2OP1=* 0.000 description 1
- 239000004593 Epoxy Chemical group 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MHQAANOFHCCCHP-UHFFFAOYSA-N NC(C=C1)=CCC1O Chemical compound NC(C=C1)=CCC1O MHQAANOFHCCCHP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000002743 phosphorus functional group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C07F9/6571—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 oxygen atoms as the only ring hetero atoms
- C07F9/657163—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 oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
- C07F9/657172—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 oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom the ring phosphorus atom and one oxygen atom being part of a (thio)phosphinic acid ester: (X = O, S)
-
- 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
- C07F9/6571—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 oxygen atoms as the only ring hetero atoms
- C07F9/6574—Esters of oxyacids of phosphorus
- C07F9/65746—Esters of oxyacids of phosphorus the molecule containing more than one cyclic phosphorus atom
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
A kind of preparation method and applications of the spiro-phosphate fire retardant containing DOPO and benzoxazine.Under methanol effect, 4 amino-phenols, 2 hydroxy benzaldehydes, DOPO, formaldehyde are treated different things alike synthetic intermediate I, and phosphorus oxychloride and pentaerythrite react synthetic intermediate II（Spiro-phosphate diacid chloride）, the spiro-phosphate fire retardant containing DOPO and benzoxazine that appearance is white solid powder is obtained by the reaction in intermediate I and intermediate II.The initial decomposition temperature of the fire retardant is about 320 DEG C, reaches 58% in the carbon yield of 450 DEG C of weightlessness up to 9%, 700 DEG C of fire retardant, which has preferable thermal stability, carbon yield height, good flame retardation effect, can be used for the halogen-free flameproof of polypropylene, ABS.
Description
Technical field
The invention belongs to phosphorus nitrogen cooperative resistance combustion compound technicals, and in particular to a kind of containing DOPO and benzoxazine
Spiro-phosphate fire retardant, the fire retardant have that preferable thermal stability, carbon yield be high, good flame retardation effect, can be used for polypropylene,
The halogen-free flameproof of ABS.
Background technology
There is a fire-retardant high polymer of halogen fire retardant, when burning will produce hydrogen halides and other thermal crackings with corrosivity and toxicity
Product.With the continuous enhancing of people's environmental consciousness, halogen-free flame retardants becomes the inexorable trend of fire retardant development.DOPO is novel
Flame retardant intermediate can react generation in structure containing active phosphorus-hydrogen bond to alkene, epoxy bond and the great activity of carbonyl
Many derivatives, DOPO and its derivative due in molecular structure contain cyclohexyl biphenyl and phenanthrene ring structure, especially side phosphorus group with
The mode of cyclic annular O=P-O keys introduces, higher than not cyclic organophosphorus ester thermal stability and chemical stability, and flame retardant property is more
It is good, and Halogen, smokeless, environmental protection, it is not easy to migrate.However DOPO monomers be directly used in high molecular material it is fire-retardant there are 180 DEG C just
The shortcomings that starting to decompose, cannot meet the processing temperature of most polymer material.And spiro-phosphate has higher thermal decomposition temperature
Degree, coke is completely formed to 400 DEG C, which remains to anti-oxidant at 600 DEG C of even higher temperature, itself can also be used as resistance
Fire agent.Spiro-phosphate fire retardant plays fire-retardant, plasticising double effects, and smaller to environmental hazard, the heat that can effectively reduce material is released
It puts rate, reduces toxic gas and smoke release, be excellent halogenated flame retardant substitute products, but its application and development are relatively slow
Slowly, it is few the product commercially produced has been put into, there are synthesis technology complexity, low yield, the shortcomings of price is high.
Invention content
It is an object of the invention to overcome above-mentioned shortcoming in the prior art, provide it is a kind of it is simple for process, be produced into
This low, disadvantage for overcoming spiro-phosphate price high reacts (the loop coil phosphorus of synthetic intermediate II by phosphorus oxychloride and pentaerythrite
Acid esters diacid chloride), treated different things alike synthetic intermediate I using 4-aminophenol, Benzaldehyde,2-hydroxy, DOPO, formaldehyde, intermediate I with
Intermediate II reaction generates the novel spiro-phosphate fire retardant containing DOPO and benzoxazine of excellent flame retardancy.
The purpose of the present invention is be achieved：A kind of spiro-phosphate fire retardant containing DOPO and benzoxazine, the chemical combination
Object has following chemical structural formula：
The preparation method of spiro-phosphate fire retardant containing DOPO and benzoxazine：
A：It by 4-aminophenol, Benzaldehyde,2-hydroxy, DOPO, is dissolved in organic solvent, is passed through nitrogen, normal-temperature reaction 10-
After 15 hours, be added formaldehyde, normal-temperature reaction 4-10 hour, then be warming up to 60-75 DEG C react 10-15h after, reaction solution is poured into water
In, a large amount of white solids are precipitated, filters, dries to obtain intermediate I, reaction equation is as follows：
B：Pentaerythrite, phosphorus oxychloride, organic solvent are added to equipped with stirring, reflux condensing tube, hydrogen chloride absorption dress
In the flask set, stirring heats up 50 DEG C~90 DEG C, and reaction to no hydrogen chloride is released, cold filtration, dichloromethane washing, drying
Intermediate II is obtained afterwards, and reaction equation is as follows：
C：Organic solvent is added into intermediate II, intermediate I is added after stirring to dissolve, is added dropwise under ice cooling, 4
Acid binding agent after being added dropwise, is heated to 130-170 DEG C, steams solvent after the completion of reaction, filter, recrystallize to obtain white crystals powder
End, reaction equation are as follows：
Spiro-phosphate fire retardant containing DOPO and benzoxazine.
Spiro-phosphate fire retardant containing DOPO and benzoxazine is as polypropylene, the phosphorus nitrogen cooperative flame retardant additive of ABS
Application.
In the step A, organic solvent is any one of methanol, ethyl alcohol, acetonitrile.
In further preferably step A, reaction temperature is 65-70 DEG C after heating；The solvent is methanol.
In the step A, the ratio between 4-aminophenol, amount of substance of Benzaldehyde,2-hydroxy, DOPO are 1：1.0-1.4
The weight of organic solvent be 4-aminophenol, 5-8 times of Benzaldehyde,2-hydroxy, DOPO total weights.
In the step B, pentaerythrite, phosphorus oxychloride the ratio between the amount of substance be 1：2.0-2.2 described is organic molten
Agent is acetonitrile, and addition weight is 5-9 times with pentaerythrite, phosphorus oxychloride total weight.
In the step C, the ratio between intermediate II, amount of substance of intermediate I are 1：2.0-2.5, the weight of organic solvent
Amount be intermediate I, 6-10 times of intermediate II total weight.
Organic solvent described in the step C is n,N-dimethylacetamide, n,N-Dimethylformamide, dimethyl sulfoxide
Any one of, acid binding agent is any one of triethylamine, n,N-Dimethylaniline.
In the step C, the acid binding agent is triethylamine；The solvent is n,N-Dimethylformamide.
Technical scheme of the present invention exists the spiro-phosphate fire retardant containing DOPO and benzoxazine being prepared
Polypropylene, ABS resin phosphorus nitrogen cooperative flame retardant additive application.
Beneficial effects of the present invention are as follows：
(1) fire retardant provided by the invention be will contain double DOPO, benzoxazine structural unit is introduced into spiro-phosphate
It closes in object, achievees the purpose that phosphorus nitrogen cooperative flame retardant, there is higher phosphorus content, nitrogen content, heat resistance and high temperature charring rate, it both can be with
It as reactive flame retardant, is linked into polypropylene and is used, and additive flame retardant can be used as, for meeting to fire-retardant
The halogen-free flameproof of the higher ABS of agent heat resistant requirements.
(2) product that synthesizes of the present invention, thermostabilization is good, and fire-retardant rate is high, and purity is up to 98.5%.
(3) raw material used in the present invention is easy to get, technique is advanced, is easy to industrialized production.
Specific implementation mode
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 range of example statement.
To develop the higher fire retardant of flame retarding efficiency, by the core of double DOPO, benzoxazine, spiro-phosphate compound
Structure fragment rationally assemble and modify, and synthesizes the composite fire retardant of the spiro-phosphate containing DOPO and benzoxazine.
Embodiment 1：
A kind of preparation method of the spiro-phosphate fire retardant containing DOPO and benzoxazine, step are：
4-aminophenol 13.10g is added in the flask equipped with blender, reflux condensing tube and device for absorbing tail gas
(0.12mol), Benzaldehyde,2-hydroxy 14.66g (0.12mol) DOPO 25.94g (0.12mol), 250mL methanol.Nitrogen is passed through,
After normal-temperature reaction 10h, 37% formaldehyde 9.84g (0.12mol), normal-temperature reaction 6h are added, is warming up to 65-70 DEG C, reaction
12h.After reaction, reaction solution is poured into 300mL water, a large amount of white solids is precipitated, filtered, be dried in vacuo to obtain intermediate I,
Yield 91.2%.
In the flask equipped with blender, reflux condensing tube and device for absorbing tail gas, it is separately added into 27.24g (0.20mol)
Pentaerythrite, 300mL acetonitriles and 91.2g (0.60mol) phosphorus oxychloride (POCl3), 75 DEG C of -80 DEG C of reaction 12h, up to no chlorination
Hydrogen generates；It is cooled to room temperature, filters, washed respectively with dichloromethane, ethyl alcohol, be dried in vacuo to obtain intermediate II, white is solid
Body powder, yield 72.6%.
In the flask equipped with n,N-Dimethylformamide 200mL, intermediate II 14.85g (0.05mol) is added), stirring
It makes it dissolve, 44.11g (0.10mol) intermediate I is added portionwise, under ice cooling, 4,12.15g (0.12mo1) three second is added dropwise
Amine, stirring, is added dropwise, and is gradually heated to 145-150 DEG C, steams n,N-Dimethylformamide after the completion of reaction, pour into 150mL
In water, target compound, white solid powder, yield 86.2% are recrystallized to obtain with acetonitrile-water mixed solvent.
The chemical equation of prepare compound of the present invention is：
Spiro-phosphate fire retardant containing DOPO and benzoxazine.
Spiro-phosphate fire retardant produced by the present invention containing DOPO and benzoxazine, appearance is white solid powder, should
The initial decomposition temperature of compound is about 320 DEG C, reaches 58% in the carbon yield of 450 DEG C of weightlessness up to 9%, 700 DEG C of fire retardant, this
Fire retardant has preferable thermal stability, carbon yield high.High temperature carbon yield is higher, and flame retardant effect is also better, therefore the fire retardant
With preferable flame retardant effect.
The analysis result of spiro-phosphate fire retardant produced by the present invention containing DOPO and benzoxazine is as follows：
Its appearance of compound is white solid, results of IR：FT-IR(KBr),v/cm-1：3009 be nearby benzene
Ring C-H stretching vibration peaks, 1564 be nearby P-Ph stretching vibration peaks, and 1163,921 be nearby P-O-Ph stretching vibration peaks, 1232
It is nearby P=O stretching vibration peaks；1600cm-1, 1581cm-1, 1463cm-1For the absorption peak of phenyl ring, 842cm-1In spirane structure
The skeletal vibration peak of pentaerythrite；Nuclear magnetic resonance spectroscopy analysis result：1H NMR(DMSO-d6,400MHz):7.65-7.52(m,
5H,Ar-H),7.41-7.32(m,6H,Ar-H),7.15-7.02(m,8H,Ar-H),6.93-6.82(m,7H,Ar-H),6.72-
6.53 (m, 6H, Ar-H), 5.11 (s, 2H, PCHN), 5.03 (s, 4H, NCH2O), 4.23 (d, J=7.5,8H, OCH2).
Embodiment 2：
Solvent changes n,N-dimethylacetamide, other same examples one, target compound yield 80.5% into.
Solvent changes dimethyl sulfoxide (DMSO), other same examples one, target compound yield 81.7% into.
Embodiment 3：
Acid binding agent triethylamine changes n,N-Dimethylaniline, other same examples one, target compound yield 83.6% into.
Embodiment 4：
The amount of intermediate I is increased into 46.31g (0.105mol), other same examples one, target compound yield
88.3%.
Embodiment 5：
The amount of intermediate I is increased into 48.51g (0.11mol), other same examples one, target compound yield
91.4%.
Embodiment 6：
The amount of intermediate I is increased into 50.72g (0.115mol), other same examples one, target compound yield
89.3%.
Embodiment 7：
The amount of intermediate I is increased into 52.82g (0.12mol), other same examples one, target compound yield
83.1%.
Embodiment 8：
The amount of intermediate I is increased into 55.13g (0.125mol), other same examples one, target compound yield
81.3%.
Spiro-phosphate fire retardant provided by the invention containing DOPO and benzoxazine is assisted as the phosphorus nitrogen of polypropylene, ABS
Application with flame-retardant additive is as follows：
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 type Vertical combustion instruments carry out the test of UL94 vertical combustion performances, measurement result such as following table
Shown in 1-2.
1 embodiment of the present invention of table, the 1 polyacrylic effect of fire retardant
The effect of 2 embodiment of the present invention of table, 1 fire retardant ABS
Claims (10)
1. a kind of spiro-phosphate fire retardant containing DOPO and benzoxazine, which is characterized in that its chemical structural formula is as follows：
Spiro-phosphate structure of the fire retardant containing DOPO and benzoxazine.
2. preparing the synthetic method of the spiro-phosphate fire retardant described in claim 1 containing DOPO and benzoxazine, feature
It is, includes the following steps：
A：It by 4-aminophenol, Benzaldehyde,2-hydroxy, DOPO, is dissolved in organic solvent, normal-temperature reaction is added after 10-15 hours
Formaldehyde, normal-temperature reaction 4-10 hours, then after being warming up to 60-75 DEG C of reaction 10-15h, reaction solution is poured into water, is precipitated a large amount of white
Color solid filters, dries to obtain intermediate I, reaction equation is as follows：
B：Pentaerythrite, phosphorus oxychloride, organic solvent are added to equipped with stirring, reflux condensing tube, hydrogen chloride absorption device
In flask, stirring heats up 50 DEG C~90 DEG C, and reaction to no hydrogen chloride is released, cold filtration, after dichloromethane washing, drying
Intermediate II, reaction equation are as follows：
C：Organic solvent is added into intermediate II, intermediate I is added after stirring to dissolve, is added dropwise ties up acid under ice cooling, 4
Agent after being added dropwise, is heated to 130-170 DEG C, steams solvent after the completion of reaction, filter, recrystallize to obtain white crystalline powder, instead
Answer equation as follows：
Spiro-phosphate fire retardant containing DOPO and benzoxazine.
3. the preparation method of the spiro-phosphate fire retardant according to claim 2 containing DOPO and benzoxazine, feature
It is：In step A, organic solvent is any one of methanol, ethyl alcohol, acetonitrile.
4. the preparation method of the spiro-phosphate fire retardant according to claim 3 containing DOPO and benzoxazine, feature
It is：In step A, reaction temperature is 65-70 DEG C after heating；The solvent is methanol.
5. the preparation method of the spiro-phosphate fire retardant according to claim 2 containing DOPO and benzoxazine, feature
It is：In step A, the ratio between 4-aminophenol, amount of substance of Benzaldehyde,2-hydroxy, DOPO are 1：1.0-1.4 organic solvent
Weight be 4-aminophenol, 5-8 times of Benzaldehyde,2-hydroxy, DOPO total weights.
6. the preparation method of the spiro-phosphate fire retardant according to claim 2 containing DOPO and benzoxazine, feature
It is：In step B, pentaerythrite, phosphorus oxychloride the ratio between the amount of substance be 1：2.0-2.2, the organic solvent are acetonitriles,
It adds weight as 5-9 times with pentaerythrite, phosphorus oxychloride total weight.
7. the preparation method of the spiro-phosphate fire retardant according to claim 2 containing DOPO and benzoxazine, feature
It is：In step C, the ratio between intermediate II, amount of substance of intermediate I are 1：The weight of 2.0-2.5, organic solvent are intermediate
I, 6-10 times of intermediate II total weight.
8. the preparation method of the spiro-phosphate fire retardant according to claim 2 containing DOPO and benzoxazine, feature
It is：Organic solvent described in step C is any in n,N-dimethylacetamide, n,N-Dimethylformamide, dimethyl sulfoxide
Kind, acid binding agent is any one of triethylamine, n,N-Dimethylaniline.
9. the preparation method of the spiro-phosphate fire retardant according to claim 8 containing DOPO and benzoxazine, feature
It is：In step C, the acid binding agent is triethylamine；The solvent is n,N-Dimethylformamide.
10. what is be prepared described in any one described in claim 2-9 hinders containing the spiro-phosphate of DOPO and benzoxazine
Fire application of the agent in polypropylene, the phosphorus nitrogen cooperative flame retardant additive of ABS resin.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109972389A (en) * | 2019-04-09 | 2019-07-05 | 新昌县高纤纺织有限公司 | Fire-retardant crease-shedding finishing agent used for textiles and preparation method thereof, application |
| CN110041532A (en) * | 2019-05-21 | 2019-07-23 | 安徽大学 | A kind of novel attapulgite soil matrix composite flame-retardant agent and its preparation and application containing spirane structure |
| CN110573553A (en) * | 2017-04-25 | 2019-12-13 | 罗地亚经营管理公司 | A flame retardant polymer; method for preparing the same and thermoplastic polymer composition comprising the same |
| CN117261378A (en) * | 2023-11-23 | 2023-12-22 | 四川烈火胜服科技有限公司 | Fireproof heat-insulating composite fabric and application thereof in firefighter uniform |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757579A (en) * | 2012-07-19 | 2012-10-31 | 三峡大学 | Oxa-phosphaphenanthrene flame retardant containing cyclotriphosphonitrile structure, and preparation method and application thereof |
| CN103012484A (en) * | 2012-12-24 | 2013-04-03 | 清华大学深圳研究生院 | Phosphorous benzoxazine resin, preparation method and application |
| CN103254466A (en) * | 2013-05-24 | 2013-08-21 | 华南理工大学 | Spiro-cage-structure-containing phosphate halogen-free flame retardant and preparation method thereof |
| CN104774343A (en) * | 2015-03-10 | 2015-07-15 | 三峡大学 | Phenyl phosphate flame retardant containing DOPO, and preparation method and application thereof |
-
2018
- 2018-04-04 CN CN201810301027.2A patent/CN108586803A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102757579A (en) * | 2012-07-19 | 2012-10-31 | 三峡大学 | Oxa-phosphaphenanthrene flame retardant containing cyclotriphosphonitrile structure, and preparation method and application thereof |
| CN103012484A (en) * | 2012-12-24 | 2013-04-03 | 清华大学深圳研究生院 | Phosphorous benzoxazine resin, preparation method and application |
| CN103254466A (en) * | 2013-05-24 | 2013-08-21 | 华南理工大学 | Spiro-cage-structure-containing phosphate halogen-free flame retardant and preparation method thereof |
| CN104774343A (en) * | 2015-03-10 | 2015-07-15 | 三峡大学 | Phenyl phosphate flame retardant containing DOPO, and preparation method and application thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110573553A (en) * | 2017-04-25 | 2019-12-13 | 罗地亚经营管理公司 | A flame retardant polymer; method for preparing the same and thermoplastic polymer composition comprising the same |
| CN109972389A (en) * | 2019-04-09 | 2019-07-05 | 新昌县高纤纺织有限公司 | Fire-retardant crease-shedding finishing agent used for textiles and preparation method thereof, application |
| CN109972389B (en) * | 2019-04-09 | 2021-12-17 | 广州市弘邦纺织用品制造有限公司 | Flame-retardant crease-resistant finishing agent for textiles and preparation method and application thereof |
| CN110041532A (en) * | 2019-05-21 | 2019-07-23 | 安徽大学 | A kind of novel attapulgite soil matrix composite flame-retardant agent and its preparation and application containing spirane structure |
| CN110041532B (en) * | 2019-05-21 | 2021-08-31 | 安徽大学 | Attapulgite-based composite flame retardant containing spiro structure and preparation and application thereof |
| CN117261378A (en) * | 2023-11-23 | 2023-12-22 | 四川烈火胜服科技有限公司 | Fireproof heat-insulating composite fabric and application thereof in firefighter uniform |
| CN117261378B (en) * | 2023-11-23 | 2024-01-23 | 四川烈火胜服科技有限公司 | Fireproof heat-insulating composite fabric and application thereof in firefighter uniform |
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