CN105732705A - Phosphorus-nitrogen-containing flame-retardant monomer and preparation method thereof - Google Patents
Phosphorus-nitrogen-containing flame-retardant monomer and preparation method thereof Download PDFInfo
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- CN105732705A CN105732705A CN201610054497.4A CN201610054497A CN105732705A CN 105732705 A CN105732705 A CN 105732705A CN 201610054497 A CN201610054497 A CN 201610054497A CN 105732705 A CN105732705 A CN 105732705A
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- phosphorus
- containing flame
- reaction
- binding agent
- nitrogen containing
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 62
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 45
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 239000000178 monomer Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000002253 acid Substances 0.000 claims abstract description 20
- 239000011230 binding agent Substances 0.000 claims abstract description 20
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims abstract description 18
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007806 chemical reaction intermediate Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000000605 extraction Methods 0.000 claims abstract description 12
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 12
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 8
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 4
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 8
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract 2
- 238000004140 cleaning Methods 0.000 abstract 2
- 238000000746 purification Methods 0.000 abstract 2
- 238000007259 addition reaction Methods 0.000 abstract 1
- 238000003287 bathing Methods 0.000 abstract 1
- 238000003760 magnetic stirring Methods 0.000 abstract 1
- 229920000098 polyolefin Polymers 0.000 abstract 1
- 230000000979 retarding effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 7
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 239000011574 phosphorus Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- -1 nitrogen-containing compound Chemical class 0.000 description 4
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000007334 copolymerization reaction Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000004679 31P NMR spectroscopy Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004079 fireproofing Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000005395 methacrylic acid group Chemical group 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000001629 suppression Effects 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
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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/247—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aromatic amines (N-C aromatic linkage)
-
- 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
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2408—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyalkyl compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The invention discloses a phosphorus-nitrogen-containing flame-retardant monomer and a preparation method thereof, and relates to a flame-retardant material. The preparation method comprises: adding p-phenylenediamine into a container containing a solvent, performing magnetic stirring until the p-phenylenediamine is dissolved, and adding carbon tetrachloride and an acid-binding agent; dissolving diethyl phosphite with a solvent, then adding the dissolved diethyl phosphite into the container for reaction, filtering the reaction solution, then separating the acid-binding agent hydrochloride, and performing extraction cleaning, rotary evaporation, purification and drying to obtain a reaction intermediate compound; and dissolving the reaction intermediate compound in a solvent, adding an acid-binding agent, performing water bathing, adding methacryloyl chloride for reaction, performing filtration, then separating the acid-binding agent hydrochloride, and performing extraction cleaning, rotary evaporation, purification and drying to obtain the phosphorus-nitrogen-containing flame-retardant monomer. The reaction can be performed at room temperature, and is easy to control and simple to operate. The phosphorus-nitrogen-containing flame-retardant monomer can be homo-polymerized into a macromolecular flame retardant, can be co-polymerized into a macromolecular flame retardant with other monomers, and can be used as a reactant to perform double-bond addition reaction. The phosphorus-nitrogen-containing flame-retardant monomer can be used for inflaming retarding of polyolefin type or epoxy resin materials.
Description
Technical field
The present invention relates to fire proofing, especially relate to a kind of phosphorus-nitrogen containing flame-retardant monomer and preparation method thereof.
Background technology
Macromolecular material is prone to processing, wide in variety, superior performance, low price, and its goods are widely used in the various aspects of production, life.But major part Flame Retardancy can be poor, endanger life and the property safety of people.The fire-retardant of high molecular products becomes the problem needing solution badly.
Conventional halogen fire retardant generates more cigarette and discharges irritant and corrosive gas, contaminated environment when burning, is detrimental to health.European Union prohibitted the use of halogen flame in 2006.Fire retardant towards non-halogen, press down the directions such as fuming, non-toxic gas, cooperative flame retardant and develop.
Can producing following process in the fire-retardant process of phosphorus flame retardant, the thermal loss that causes such as the suppression of flame, molten drop, the surface interruption that phosphoric acid causes, the accumulation of acid catalysis layer of charcoal and carbon deposit prevent the further oxidation etc. of charcoal.Corrosivity in its catabolite and combustion product, Toxic are little.
The non-flammable gases such as nitrogen, ammonia, carbon dioxide, degree of depth nitrogen oxides are discharged after decomposes during nitrogenated flame retardant burning, the supply of oxygen of these nonflammable gas occludings, taking away major part heat simultaneously, greatly reducing the surface temperature of material, thus reaching flame retardant effect.
Improving macromolecular material fire resistance, phosphorus nitrogen cooperative flame retardant is subject to the attention of researcher.Chinese patent CN104592300A discloses a kind of phosphor nitrogen combustion inhibitor and preparation method thereof, and this phosphor nitrogen combustion inhibitor is the little molecule fire retardant of addition type, and its preparation process with part side reaction, can cause product purity to decline.Chinese patent CN104311818A discloses a kind of phosphorous, nitrogen aggretion type fire retardant and preparation method thereof, and this fire retardant is that the phosphorus-containing compound of two degrees of functionality forms with the nitrogen-containing compound polycondensation of three-functionality-degree, and preparation process produces more micromolecular compound.Open a kind of fire-retardant block copolymer of phosphorus-nitrogen containing of Chinese patent CN104262553A and preparation method thereof, introduces fire retardant, the method scalable phosphorus nitrogen content ratio by twice polymerization by phosphorus, nitrogen element.But existing phosphorus-nitrogen containing fire retardant, the report about phosphorus-nitrogen containing flame-retardant monomer is less.
Summary of the invention
It is an object of the invention to provide a kind of phosphorus-nitrogen containing flame-retardant monomer and preparation method thereof.
The chemical structural formula of described phosphorus-nitrogen containing flame-retardant monomer is as follows:
The syntheti c route of described phosphorus-nitrogen containing flame-retardant monomer is as follows:
The preparation method of described phosphorus-nitrogen containing flame-retardant monomer, comprises the following steps:
1) taking p-phenylenediamine to join equipped with in the container of solvent, magnetic agitation is dissolved to p-phenylenediamine, adds carbon tetrachloride and acid binding agent；Being dissolved by diethyl phosphite solvent, then diethyl phosphite adds reaction in container, separated by acid binding agent hydrochlorate after reacting liquid filtering, extraction is washed, rotary evaporation, purifies, namely obtains reaction intermediate compound after drying；
2) by step 1) the reaction intermediate compound that obtains is dissolved in solvent, adds acid binding agent, water-bath, add methacrylic chloride reaction, being separated by acid binding agent hydrochlorate after filtration, extraction is washed, rotary evaporation, purifies, namely obtains phosphorus-nitrogen containing flame-retardant monomer after drying.
In step 1) in, described solvent is selected from the one in DMF, oxolane, dichloromethane, acetonitrile, chloroform etc.；Described acid binding agent is selected from the one in triethylamine, pyridine, sodium bicarbonate, potassium carbonate etc.；The time of described reaction can be 10～24h；Described p-phenylenediamine, carbon tetrachloride, acid binding agent, diethyl phosphite mol ratio can be 1: (1～3): (1～3): (1～1.5)；Diethyl phosphite is added in container by the described available constant pressure funnel of reaction in container that added by diethyl phosphite.
In step 2) in, described solvent is selected from the one in ethyl acetate, acetonitrile, DMF, dichloromethane, chloroform, toluene etc.；Described acid binding agent is selected from the one in triethylamine, pyridine, sodium bicarbonate, potassium carbonate etc.；The time of described reaction can be 8～16h；Described midbody compound, acid binding agent, methacrylic chloride mol ratio can be 1: (1～3): (1～1.5).
Phosphorus-nitrogen containing flame-retardant monomer of the present invention dissolves in multi-solvents, and selectivity is big, and reaction condition is gentle, it is not necessary to temperature reaction.This monomer contains phosphorus and nitrogen element, is improved the fire retardancy of macromolecular material by cooperative flame retardant effect.This monomer for can homopolymerization be macromolecular fire retardant, can be macromolecular fire retardant with the monomer copolymerization such as acrylic compounds, methacrylic, methacryl amine, and contained double bond with other micromolecular compound generation additive reaction, can expand its use scope.
The macromolecular fire retardant of phosphorus-nitrogen containing flame-retardant monomer homopolymerization of the present invention or copolymerization gained can add the polymer such as epoxy resin, polypropylene, polyethylene to, while improving the fire resistance of material, it is possible to improves fire retardant and the matrix compatibility.
The reaction of the present invention just can carry out in room temperature, it is easy to controls, simple to operate.This phosphorus-nitrogen containing flame-retardant monomer is applied widely, can homopolymerization be macromolecular fire retardant, it is possible to be macromolecular fire retardant with other monomer copolymerizations, can carry out the additive reaction of double bond as reactant.Can be used for the fire-retardant of TPO and epoxide resin material.
Accompanying drawing explanation
Fig. 1 is the phosphorus-nitrogen containing flame-retardant monomer that embodiment 1 is obtained1HNMR nuclear magnetic spectrogram.
Fig. 2 is the phosphorus-nitrogen containing flame-retardant monomer that embodiment 1 is obtained31PNMR nuclear magnetic spectrogram.
Detailed description of the invention
The present invention is further illustrated with accompanying drawing by the examples below.
Embodiment 1
1) p-phenylenediamine 1.08g (0.01mol) is taken, join equipped with N, in the container of dinethylformamide, magnetic agitation is dissolved to p-phenylenediamine, adds carbon tetrachloride 1.54g (0.01mol) and triethylamine 1.01g (0.01mol).Weigh diethyl phosphite 1.38g (0.01mol), dissolve with a small amount of DMF, with constant pressure funnel, diethyl phosphite is instilled in container.Normal-temperature reaction 16h.Filter and triethylamine hydrochloride is separated.Extraction is washed, after rotary evaporation, is purified, is drying to obtain reaction intermediate compound.
2) reaction intermediate compound 1.22g (0.005mol) is dissolved in ethyl acetate, adds triethylamine 1.01g (0.01mol), water-bath, instill methacrylic chloride 0.5225g (0.005mol), react 8h.Filter and triethylamine hydrochloride is separated.Extraction is washed, after rotary evaporation, is purified, namely obtains this phosphorus-nitrogen containing flame-retardant monomer after drying.Gained phosphorus-nitrogen containing flame-retardant monomer is carried out the sign of proton nmr spectra (Fig. 1) and phosphorus spectrum (Fig. 2).
Fig. 1 is phosphorus-nitrogen containing flame-retardant monomer1HNMR nuclear magnetic spectrogram, chemical shift 5.45ppm and 5.76ppm is double bond proton peak, and chemical shift 6.93ppm and 7.47ppm is phenyl ring proton peak, and chemical shift 5.45ppm and 5.76ppm is NH proton peak, and chemical shift 3.99ppm is OCH2Proton peak, chemical shift 1.94ppm is the methyl proton peak that is connected with double bond, and chemical shift 1.18ppm is the methyl proton peak being connected with methylene, and chemical shift 2.5ppm is imaging reagent DMSO solvent peak.And each position integral area ratio is consistent with actual hydrogeneous number ratio.Fig. 2 is phosphorus-nitrogen containing flame-retardant monomer31PNMR nuclear magnetic spectrogram, phosphorus spectrum is for unimodal.With phosphorus spectrum, hydrogen spectrum illustrates that phosphorus-nitrogen containing flame-retardant monomer of the present invention successfully synthesizes.
Embodiment 2
1) taking p-phenylenediamine 1.62g (0.015mol), join equipped with in the container of oxolane, magnetic agitation is dissolved to p-phenylenediamine, adds carbon tetrachloride 4.62g (0.03mol) and pyridine 2.37g (0.01mol).Weigh diethyl phosphite 2.07g (0.015mol), dissolve with a small amount of oxolane, with constant pressure funnel, diethyl phosphite is instilled in container.Normal-temperature reaction 12h.Filter and pyridine hydrochloride is separated.Extraction washes, after rotary evaporation.Purify, be drying to obtain reaction intermediate compound.
2) reaction intermediate compound 2.44g (0.01mol) is dissolved in dichloromethane, adds triethylamine 2.02g (0.02mol), water-bath, instill methacrylic chloride 1.045g (0.01mol), react 10h.Filter and triethylamine hydrochloride is separated.Extraction is washed, after rotary evaporation, is purified, namely obtains this phosphorus-nitrogen containing flame-retardant monomer after drying.
Embodiment 3
1) taking p-phenylenediamine 0.54g (0.005mol), join equipped with in the container of chloroform, magnetic agitation is dissolved to p-phenylenediamine, adds carbon tetrachloride 2.31g (0.015mol) and sodium bicarbonate 1.68g (0.01mol).Weigh diethyl phosphite 0.69g (0.005mol), dissolve with a small amount of chloroform, with constant pressure funnel, diethyl phosphite is instilled in container.Normal-temperature reaction 20h.Filter and sodium chloride is separated.Extraction is washed, after rotary evaporation, is purified, is drying to obtain reaction intermediate compound.
2) reaction intermediate compound 1.22g (0.005mol) is dissolved in acetonitrile, adds pyridine 0.79g (0.01mol), water-bath, instill methacrylic chloride 0.627g (0.006mol), react 12h.Filter and pyridine hydrochloride is separated.Extraction is washed, after rotary evaporation, is purified, namely obtains this phosphorus-nitrogen containing flame-retardant monomer after drying.
Claims (10)
1. a phosphorus-nitrogen containing flame-retardant monomer, it is characterised in that its chemical structural formula is as follows:
2. the syntheti c route of a kind of phosphorus-nitrogen containing flame-retardant monomer as claimed in claim 1 is as follows:
3. the preparation method of a kind of phosphorus-nitrogen containing flame-retardant monomer as claimed in claim 1, it is characterised in that comprise the following steps:
1) taking p-phenylenediamine to join equipped with in the container of solvent, magnetic agitation is dissolved to p-phenylenediamine, adds carbon tetrachloride and acid binding agent；Being dissolved by diethyl phosphite solvent, then diethyl phosphite adds reaction in container, separated by acid binding agent hydrochlorate after reacting liquid filtering, extraction is washed, rotary evaporation, purifies, namely obtains reaction intermediate compound after drying；
2) by step 1) the reaction intermediate compound that obtains is dissolved in solvent, adds acid binding agent, water-bath, add methacrylic chloride reaction, being separated by acid binding agent hydrochlorate after filtration, extraction is washed, rotary evaporation, purifies, namely obtains phosphorus-nitrogen containing flame-retardant monomer after drying.
4. the preparation method of a kind of phosphorus-nitrogen containing flame-retardant monomer as claimed in claim 3, it is characterised in that in step 1) in, described solvent one in DMF, oxolane, dichloromethane, acetonitrile, chloroform.
5. the preparation method of a kind of phosphorus-nitrogen containing flame-retardant monomer as claimed in claim 3, it is characterised in that in step 1) in, described acid binding agent one in triethylamine, pyridine, sodium bicarbonate, potassium carbonate.
6. the preparation method of a kind of phosphorus-nitrogen containing flame-retardant monomer as claimed in claim 3, it is characterised in that in step 1) in, the time of described reaction is 10～24h.
7. the preparation method of a kind of phosphorus-nitrogen containing flame-retardant monomer as claimed in claim 3, it is characterized in that in step 1) in, described p-phenylenediamine, carbon tetrachloride, acid binding agent, diethyl phosphite mol ratio be 1: (1～3): (1～3): (1～1.5)；Diethyl phosphite is added in container by the described available constant pressure funnel of reaction in container that added by diethyl phosphite.
8. the preparation method of a kind of phosphorus-nitrogen containing flame-retardant monomer as claimed in claim 3, it is characterised in that in step 2) in, described solvent one in ethyl acetate, acetonitrile, DMF, dichloromethane, chloroform, toluene.
9. the preparation method of a kind of phosphorus-nitrogen containing flame-retardant monomer as claimed in claim 3, it is characterised in that in step 2) in, described acid binding agent one in triethylamine, pyridine, sodium bicarbonate, potassium carbonate；The time of described reaction can be 8～16h.
10. the preparation method of a kind of phosphorus-nitrogen containing flame-retardant monomer as claimed in claim 3, it is characterised in that in step 2) in, described midbody compound, acid binding agent, methacrylic chloride mol ratio be 1: (1～3): (1～1.5).
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