CN106478729A - Six（P-aminophenyl epoxide）The preparation method of three phosphonitrile of ring - Google Patents
Six（P-aminophenyl epoxide）The preparation method of three phosphonitrile of ring Download PDFInfo
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- CN106478729A CN106478729A CN201610884928.XA CN201610884928A CN106478729A CN 106478729 A CN106478729 A CN 106478729A CN 201610884928 A CN201610884928 A CN 201610884928A CN 106478729 A CN106478729 A CN 106478729A
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- phosphonitrile
- ring
- preparation
- aminophenyl epoxide
- hexachlorocyclotriph
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- 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 System
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6581—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and nitrogen atoms with or without oxygen or sulfur atoms, as ring hetero atoms
- C07F9/65812—Cyclic phosphazenes [P=N-]n, n>=3
- C07F9/65815—Cyclic phosphazenes [P=N-]n, n>=3 n = 3
Abstract
The present invention provides a kind of preparation method of six (p-aminophenyl epoxide) three phosphonitrile of ring, comprises the following steps：A () acamol, hexachlorocyclotriph,sphazene and inorganic alkaline compound, in a solvent, back flow reaction to hexachlorocyclotriph,sphazene disappears, and stops heating, is cooled to 05 DEG C and suction filtration, and filter cake is washed with water and dried and obtains intermediate product；B intermediate product is added in the mixed solution of water and ethanol by (), add alkali metal hydroxide, and back flow reaction to raw material disappears, and is cooled to 05 DEG C and suction filtration, is obtained the crude product that filter cake is the product；C () adds crude product to water in, it is heated to backflow, acid solution is added to clarify to solution, after activated carbon decolorizing, adjusted to pH >=9 with alkali lye at 05 DEG C, separate out solid, suction filtration,, through washing and drying to obtain described six (p-aminophenyl epoxide) three phosphonitrile of ring, the method raw material is simple and easy to get, low price for filter cake；Course of reaction and post processing simplicity, it is easy to industrialized production and overall yield of reaction height.
Description
Technical field
The present invention relates to a kind of method of six (p-aminophenyl epoxide) three phosphonitrile of ring.
Background technology
Polyphosphazene compound as a kind of full phosphorus azacyclo- non-co- compound conjugate, with its unique physical and chemical performance as state
Inside and outside research worker is attracted attention, and just has related foreign countries' monograph to come out early in 20 century 70s.Recently as domestic material
Research work gradually deeply, the research for polyphosphazene material starts gradually to develop.While having in polyphosphazene molecular structure
The phosphorus nitrogen of high-load, the collaboration system for thus constituting give its excellent fire resistance, its limited oxygen index up to 27-65, this
Outer polyphosphazene compound also has excellent photostability and a heat endurance, good high and low temperature resistance, and smoke amount is few, and nothing is rotten
Corrosion gas is released, and the advantages of the gas toxicity of releasing is relatively low, additionally has oil resistant and chemicals-resistant characteristic, water-fast and resistance to molten
Agent characteristic, these superior performances cause such material to lead in military affairs, Aero-Space ablation resistant material, textile, plastic flame
Domain has great application prospect.
Six (p-aminophenyl epoxide) three phosphonitrile of ring is one kind of three phosphonitrile of aryloxy group class ring, due to introducing phenyl ring in structure
Structure, thus its heat endurance is more more excellent than hexachlorocyclotriph,sphazene, contains multiple reactive group-NH in addition in its structure2,
Therefore other groups can be further introduced into as reaction intermediate or be applied directly as reactive fire retardant.
Three phosphonitrile of existing six (p-aminophenyl epoxide) ring is typically first with hexachlorocyclotriph,sphazene as initiation material, using right
Nitrophenol carries out affine replacement and obtains six (p-nitrophenyl epoxide) three phosphonitrile of ring to hexachlorocyclotriph,sphazene chlorine in ring atom, then
Six (p-nitrophenyl epoxide) three phosphonitrile of ring is reduced so as to obtain six (p-aminophenyl epoxide) three phosphonitrile of ring.In second step nitre
In the reduction reaction of base, conventional method is Pt/H reduction, and the reduction process method has dark thick insoluble matter to give birth in purification
Becoming and pollution, impact product purity and yield being produced to product, requirement of the method to equipment is also very high in addition.Additionally, also there is text
Offer and reported and use SnCl2/ HCl and NaBH4The reduction of nitro is carried out as reducing agent, but both post processings are all relatively
For complexity.
Content of the invention
It is an object of the invention to provide a kind of synthetic method of new six (p-aminophenyl epoxide) three phosphonitrile of ring, the method receipts
Rate is high, and post processing is simple.
The invention provides a kind of preparation method of six (p-aminophenyl epoxide) three phosphonitrile of ring, comprises the following steps：
A () acamol, hexachlorocyclotriph,sphazene and inorganic alkaline compound, in organic solvent, are warming up to
Back flow reaction, insulation reaction, monitoring reaction are disappeared to hexachlorocyclotriph,sphazene, stop heating, are cooled to 0-5 DEG C and suction filtration, filter cake
Wash with water and dry and obtain six (acetparaminosalol phenoxy group) three phosphonitrile of ring.
B () will be molten for the mixing of obtain in step (a) six three phosphonitriles of (acetparaminosalol phenoxy group) ring addition water and ethanol
In liquid, alkali metal hydroxide is added, backflow is warming up to, monitoring reaction is disappeared to raw material, and reaction is cooled to room temperature simultaneously after terminating
Suction filtration, obtains filter cake for six (p-aminophenyl epoxide) ring, three phosphonitrile crude product；
C () adds the crude product obtained in step (b) to water in, backflow is heated to, and adds acid under agitation
Liquid is clarified to solution, adds activated carbon decolorizing, suction filtration, and filtrate is adjusted to pH >=9 with alkali lye after being cooled to 0-5 DEG C, separates out solid,
Suction filtration, filter cake is through washing and drying to obtain described six (p-aminophenyl epoxide) three phosphonitrile of ring.
Organic solvent described in the step (a) is acetonitrile, acetone or toluene；Inorganic alkaline compound is alkali-metal
Hydroxide or salt of weak acid；
Further, the acamol and inorganic alkaline compound are initially charged in the step (a), in institute
Stirring at normal temperature at least 30min in organic solvent is stated, the hexachlorocyclotriph,sphazene is then dividedly in some parts, being again heated to backflow is carried out instead
Should.
Further, in the step (a), acetaminophenol, hexachlorocyclotriph,sphazene and inorganic alkaline compound put into
The mol ratio of amount is (6～10):1:(9～15).
Further, in the step (a), acetaminophenol, hexachlorocyclotriph,sphazene and inorganic alkaline compound put into
The mol ratio of amount is 9:1:12.
Further, organic solvent described in the step (a) is acetonitrile.
Further, in the step (a), inorganic alkaline compound is potassium carbonate, sodium carbonate, NaOH, potassium hydroxide
In at least one.
Further, in the step (b), the mixed solution of water and ethanol is water and ethanol with volume ratio (9～1):1 mixes
Solution after conjunction.
Further, in the step (c), acid solution is at least one in hydrochloric acid, sulfuric acid or glacial acetic acid.
Further, in the step (c), alkali lye is in the aqueous solution of NaOH or potassium hydroxide or ammoniacal liquor
At least one.
Compared with prior art, beneficial effects of the present invention have：The raw material for using is simple and easy to get, low price；Reacted
Journey and post processing simplicity, it is easy to industrialized production；Overall yield of reaction is high.
Description of the drawings
Three phosphonitrile product of Fig. 1 six (p-aminophenyl epoxide) ring1H-NMR schemes；
Three phosphonitrile product of Fig. 2 six (p-aminophenyl epoxide) ring13C-NMR schemes；
Specific embodiment
The following examples will be further described to the present invention, but not thereby limiting the invention.Following realities
Apply in example, hexachlorocyclotriph,sphazene all uses " PNC " as referred to as；Acamol, hexachlorocyclotriph,sphazene and various nothings
Machine acid, inorganic base, inorganic salts etc. are commercially available chemistry net product；Acetonitrile is for commercially available chemical pure acetonitrile and through CaH processed；
It is pure and through Na processed that toluene and acetone are commercially available chemistry.
Embodiment 1-11：
Acamol (m is weighed in proportion1), inorganic base (m2), solvent (drying) (V) is measured, stirring at normal temperature is at least
30min；Weigh PNC (m3) and be slowly added in batches, back flow reaction is warming up to, TLC monitoring is reacted, and after PNC reaction completely, stops
Heating, ice-water bath are cooled to 0-5 DEG C, filter, obtain filter cake six (acetparaminosalol phenoxy group) three phosphonitrile of ring, claim after drying
(m4).The rate of charge reaction result of different solvents and material see the table below (a note：Yield is calculated with PNC；n1、n2、n3、n4Respectively
Represent amount and six (acetparaminosalol phenoxy group) ring, the three phosphonitrile product of the material that acetaminophenol, potassium carbonate, PNC put into
Material amount)：
(a) step reaction situation under 1 different condition of table
Embodiment 12
Six (acetparaminosalol phenoxy group) ring, the three phosphonitrile 20g (19.3mmol, 1 equivalent) of above-described embodiment preparation is taken, plus
Enter 200g ethanol water (mWater:mEthanol=9:1) NaOH 5g (about 6.6 times of equivalents), is slowly added in batches, back flow reaction,
TLC monitors reaction process, and after raw material reaction is complete, ice-water bath is lowered the temperature (0-5 DEG C), separates out solid, and suction filtration is simultaneously washed filter cake, obtained
To crude product.
Crude product adds the water of about 3 times of quality, is heated to about 60 DEG C, is kept stirring for temperature and drips glacial acetic acid under stirring
(glacial acetic acid, hydrochloric acid or sulfuric acid) adds a small amount of activated carbon to being completely dissolved, and flow back at 60 DEG C 30min, and suction filtration removes deactivation while hot
Charcoal, filtrate ice-water bath are lowered the temperature (0-5 DEG C), and dropping ammoniacal liquor (ammoniacal liquor, sodium hydrate aqueous solution or potassium hydroxide aqueous solution etc.) is adjusted
PH to 9-10, separates out a large amount of solids, and suction filtration, filter cake are dry after washing to constant weight, obtain six (p-aminophenyl epoxide) three phosphorus of ring
Nitrile product 12.8g, yield 84.6%, product verify (spectrogram refer to the attached drawing 1 and accompanying drawing 2) through nuclear-magnetism.
In embodiment 12, the m of ethanol waterWater:mEthanolCan be in (1～9):Choose between 1 concentration；NaOH
Can also be substituted with other alkali metal hydroxides such as potassium hydroxide, consumption is at least 6 times equivalents, it is proposed that less than 7 times of equivalents；Ammonia
The aqueous solution can also be replaced with the aqueous solution of the alkali inorganic substance such as NaOH or potassium hydroxide, adjust pH requirement and more than 9 be
Can.
Claims (9)
1. the preparation method of six (p-aminophenyl epoxide) three phosphonitrile of ring, it is characterised in that comprise the following steps：
A () acamol, hexachlorocyclotriph,sphazene and inorganic alkaline compound, in organic solvent, are warming up to backflow
Reaction, insulation reaction, monitoring reaction are disappeared to hexachlorocyclotriph,sphazene, stop heating, are cooled to 0-5 DEG C and suction filtration, filter cake water
Wash and dry and obtain six (acetparaminosalol phenoxy group) three phosphonitrile of ring.
B obtain in step (a) six three phosphonitriles of (acetparaminosalol phenoxy group) ring are added in the mixed solution of water and ethanol by (),
Alkali metal hydroxide is added, backflow is warming up to, monitoring reaction is disappeared to raw material, and reaction is cooled to 0-5 DEG C and suction filtration after terminating,
Filter cake is obtained for six (p-aminophenyl epoxide) ring, three phosphonitrile crude product；
C () adds the crude product obtained in step (b) to water in, backflow is heated to, and adds acid solution extremely under agitation
Solution is clarified, and adds activated carbon decolorizing, suction filtration, and filtrate is adjusted to pH >=9 with alkali lye after being cooled to 0-5 DEG C, is separated out solid, is taken out
Filter, filter cake is through washing and drying to obtain described six (p-aminophenyl epoxide) three phosphonitrile of ring.
Organic solvent described in the step (a) is acetonitrile, acetone or toluene；Inorganic alkaline compound is alkali-metal hydrogen-oxygen
Compound or salt of weak acid；
2. the preparation method of a kind of six (p-aminophenyl epoxide) three phosphonitrile of ring according to claim 1, it is characterised in that institute
State in step (a) and the acamol and inorganic alkaline compound is initially charged, normal temperature is stirred in the organic solvent
At least 30min is mixed, the hexachlorocyclotriph,sphazene is then dividedly in some parts, be again heated to backflow and reacted.
3. the preparation method of a kind of six (p-aminophenyl epoxide) three phosphonitrile of ring according to claim 1, it is characterised in that institute
The mol ratio for stating acetaminophenol in step (a), hexachlorocyclotriph,sphazene and inorganic alkaline compound input amount is (6～10):
1:(6～15).
4. the preparation method of a kind of six (p-aminophenyl epoxide) three phosphonitrile of ring according to claim 3, it is characterised in that institute
The mol ratio for stating acetaminophenol in step (a), hexachlorocyclotriph,sphazene and inorganic alkaline compound input amount is 9:1:12.
5. the preparation method of one kind six (p-aminophenyl epoxide) three phosphonitrile of ring according to one of Claims 1-4, its feature
It is, organic solvent described in the step (a) is acetonitrile.
6. the preparation method of one kind six (p-aminophenyl epoxide) three phosphonitrile of ring according to one of Claims 1-4, its feature
Be, in the step (a) inorganic alkaline compound be potassium carbonate, sodium carbonate, NaOH, in potassium hydroxide at least one
Kind.
7. the preparation method of one kind six (p-aminophenyl epoxide) three phosphonitrile of ring according to one of Claims 1-4, its feature
It is, in the step (b), the mixed solution of water and ethanol is for water and ethanol with volume ratio (9～1):1 mixed solution.
8. the preparation method of one kind six (p-aminophenyl epoxide) three phosphonitrile of ring according to one of claim 1 to 6, its feature
It is, in the step (c), acid solution is at least one in hydrochloric acid, sulfuric acid or glacial acetic acid.
9. the preparation method of one kind six (p-aminophenyl epoxide) three phosphonitrile of ring according to one of claim 1 to 6, its feature
It is, in the step (c), alkali lye is at least one in the aqueous solution or ammoniacal liquor of NaOH or potassium hydroxide.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107938356A (en) * | 2017-11-30 | 2018-04-20 | 安徽中福毛纺制帽有限公司 | A kind of special crease-resistant antiflaming finishing agent of wool cap |
| CN109503953A (en) * | 2019-01-10 | 2019-03-22 | 骆玲 | A kind of capacitor polypropylene plastics shell |
| CN109749118A (en) * | 2018-12-25 | 2019-05-14 | 内蒙合成化工研究所 | A kind of preparation method of the high flame retardant polyureas aeroge based on ring phosphonitrile |
| CN113583177A (en) * | 2021-08-17 | 2021-11-02 | 安徽天润化学工业股份有限公司 | Preparation method and application of temperature-resistant and salt-resistant six-arm star polyacrylamide |
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| US20140323624A1 (en) * | 2013-04-30 | 2014-10-30 | Elite Material Co., Ltd. | Phosphazene compound having vinyl group, resin composition containing the same, and circuit board manufactured from the same |
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| US20140323624A1 (en) * | 2013-04-30 | 2014-10-30 | Elite Material Co., Ltd. | Phosphazene compound having vinyl group, resin composition containing the same, and circuit board manufactured from the same |
| CN103588815A (en) * | 2013-11-25 | 2014-02-19 | 济南泰星精细化工有限公司 | Preparation method of hexaphenoxy cyclotriphosphazene fire retardant |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107938356A (en) * | 2017-11-30 | 2018-04-20 | 安徽中福毛纺制帽有限公司 | A kind of special crease-resistant antiflaming finishing agent of wool cap |
| CN109749118A (en) * | 2018-12-25 | 2019-05-14 | 内蒙合成化工研究所 | A kind of preparation method of the high flame retardant polyureas aeroge based on ring phosphonitrile |
| CN109503953A (en) * | 2019-01-10 | 2019-03-22 | 骆玲 | A kind of capacitor polypropylene plastics shell |
| CN113583177A (en) * | 2021-08-17 | 2021-11-02 | 安徽天润化学工业股份有限公司 | Preparation method and application of temperature-resistant and salt-resistant six-arm star polyacrylamide |
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