CN103524563A - Hexaphenoxy cyclotriphosphazene decolorizing method - Google Patents
Hexaphenoxy cyclotriphosphazene decolorizing method Download PDFInfo
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- CN103524563A CN103524563A CN201310521252.4A CN201310521252A CN103524563A CN 103524563 A CN103524563 A CN 103524563A CN 201310521252 A CN201310521252 A CN 201310521252A CN 103524563 A CN103524563 A CN 103524563A
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- hexaphenoxycyclotriphosphazene
- hexachlorocyclotriphosphazene
- carclazyte
- gac
- chlorobenzene
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Abstract
The invention discloses a hexaphenoxy cyclotriphosphazene decolorizing method. According to the invention, active carbon and white clay are adopted as a combined decolorant, such that the obtained hexaphenoxy cyclotriphosphazene product is pure white crystals with substantially improved purity. Therefore, an ideal bleaching quality can be satisfied.
Description
Technical field
The invention belongs to synthesis technical field nitrogenous, phosphorus organic compound, be specifically related to the decoloring method of hexaphenoxycyclotriphosphazene.
Background technology
Hexaphenoxycyclotriphosphazene, is to take hexachlorocyclotriphosphazene as intermediate, by phenoxy group, replaces a kind of phosphazene derivative that the active chlorine atom of phosphine nitrile side group obtains, and can directly add to and in polymeric matrix, prepare fire retardant material.As add in polycarbonate and prepare flame-retardant polycarbonate material, the LOI value of material can reach 30, also can be added in PC/ABS resin, prepares fire retardation PC/ABS alloy material, and the LOI value of material can reach 26～30.Hexaphenoxycyclotriphosphazene is compared other fire retardants, there is high oxygen index, low exhaust smoke level, the advantages such as the corrosion-free and low toxicity of the gas of emitting, and good thermal stability, temperature of initial decomposition all reaches more than 300 ℃, can be applied to processing temperature is required, in higher system, can meet the processing request of new welding technology.Therefore, preparation research of phenoxy phosphazene is had to important using value.Day by day be subject to the attention of military and industrial sector.
In the synthetic method of existing hexaphenoxycyclotriphosphazene, what possess industrial value is mainly first to synthesize hexachlorocyclotriphosphazene intermediate, then makes by nucleophilic substitution reaction with sodium phenylate.First by PCl
5and NH
4cl prepares hexachlorocyclotriphosphazene under catalyst action, then hexachlorocyclotriphosphazene is dissolved in to tetrahydrofuran (THF), is added drop-wise in sodium phenylate solution, makes hexaphenoxycyclotriphosphazene.After this technique the first step has been reacted, need suction filtration, underpressure distillation chlorobenzene, with Petroleum ether extraction, through normal heptane crystallization, obtain hexachlorocyclotriphosphazene crude product again, then take that it is dissolved in tetrahydrofuran (THF) as intermediate, drop in sodium phenylate solution, react rear suction filtration, concentrated, then obtained hexaphenoxycyclotriphosphazene white crystal through NaOH solution and distilled water wash.This technical process is complicated, and cost is higher, and the hexaphenoxycyclotriphosphazene crystal making presents grey or faint yellow, and the purity of product and outward appearance are difficult to reach high-level requirement.Therefore need to decolour to hexaphenoxycyclotriphosphazene, to meet the requirement to product purity and outward appearance.Conventional hexaphenoxycyclotriphosphazene decoloring method is to adopt single gac or carclazyte at present, the adsorptive power of gac is stronger than carclazyte, in adsorbable product, the organic reagent such as residual chlorobenzene, phenol to be to improve product purity, but the two product while using separately mostly presents faint yellow.
Summary of the invention
The technical problem to be solved in the present invention is that hexaphenoxycyclotriphosphazene product purity and outward appearance can not reach the problem that high standard requires, and provides a kind of hexaphenoxycyclotriphosphazene efficient decoloring method.
Technical scheme of the present invention is: a kind of decoloring method of hexaphenoxycyclotriphosphazene, it is characterized in that, and adopt gac and carclazyte as associating discoloring agent.
As a kind of optimal way, the mass ratio of described gac and carclazyte is 1:1.
For take phosphorus pentachloride, ammonium chloride, it is starting raw material, chlorobenzene is solvent, building-up reactions through too high selection, filtration obtains the chlorobenzene solution of highly purified hexachlorocyclotriphosphazene, react in the process of preparing hexaphenoxycyclotriphosphazene with potassium phenylate again, gac and carclazyte addition are preferred, and the two total amount is for being 15～20% of hexachlorocyclotriphosphazene crude product quality, bleaching temperature 70-85 ℃.
When the present invention adopts gac+atlapulgite to decolour to hexaphenoxycyclotriphosphazene, product is pure white crystal, and purity also has clear improvement, and can reach the desirable requirement of drifting.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further; the method of preparing hexaphenoxycyclotriphosphazene in embodiment is a kind of optimal way; decoloring method of the present invention is not limited in this preparation method; those skilled in the art conceive according to the present invention this decoloring method are applied to, in hexaphenoxycyclotriphosphazene synthesis technique, all belong to protection scope of the present invention.
Embodiment 1
One, the preparation of hexachlorocyclotriphosphazene
A. under nitrogen protection, NH in mass ratio
4cl:PCl
5=(0.2～0.5): 1 feeds intake, in reactor, add successively ammonium chloride, catalyzer, pyridine, phosphorus pentachloride and chlorobenzene, the mass ratio of described ammonium chloride, composite catalyst (in described composite catalyst, mole compositely proportional of zinc chloride, iron(ic) chloride, magnesium chloride is 1:1:1), pyridine, phosphorus pentachloride and chlorobenzene is followed successively by (0.2～0.5): (0.01～0.03): (0.02～0.05): 1:(1.5～4.0).Oil bath heating, is slowly warming up to 120 ± 5 ℃ of backflows, the lower reaction 6～10 hours that refluxes, and after reaction hour, solution reaction is from the light yellow light green that becomes after for some time, and at this moment reflux temperature rises to 130 ± 5 ℃, until reaction finishes.
B. reaction finishes, and tap water is cooled to room temperature, filters out residue, obtains the chlorobenzene solution of hexachlorocyclotriphosphazene.
Two, the preparation of hexaphenoxycyclotriphosphazene
A. raw material is prepared, hexachlorocyclotriphosphazene: phenol: the mass ratio of potassium hydroxide is 1:(1.0～1.4): (0.8～1.2).
B. the preparation of phenates is first (0.5～0.7) in mass ratio: (1.0～1.4): (0.8～1.2) adds chlorobenzene, phenol and potassium hydroxide particle successively, the about 1h of stirring reaction in reactor.
C. then to the chlorobenzene solution that drips hexachlorocyclotriphosphazene synthetic in step (1) in reactor, time for adding is about 1 hour, control temperature not higher than 40 ℃, drip and finish insulation 1 hour, then gradually system temperature is risen to backflow (80～120 ℃), react 10～16 hours, reaction finishes.
D. decolouring, system is cooled to 75 ℃ of left and right, and adding mass ratio is the gac, carclazyte (total amount be hexachlorocyclotriphosphazene crude product quality 15～20%) of 1:1, is incubated 1 hour at 70-85 ℃, then filters out gac, carclazyte residue.
E. distillation, negative pressure (0.09mpa), at 80 ℃, distills chlorobenzene, the dry reuse of Calcium Chloride Powder Anhydrous for the chlorobenzene of recovery.
F. crystallization, to the ethanol (mass ratio of phenol and ethanol is 1.39:7) that adds 95% in matrass, the 0.5～1h that refluxes, fully dissolves material, then, below slow cooling to 5 ℃, filters, and in vacuum drying oven, dries, and obtains hexaphenoxycyclotriphosphazene.Total recovery reaches 76.5%, hexaphenoxycyclotriphosphazene purity >=99%, cl content≤20ppm.Gained hexaphenoxycyclotriphosphazene is pure white crystal.
Claims (3)
1. a decoloring method for hexaphenoxycyclotriphosphazene, is characterized in that, adopts gac and carclazyte as associating discoloring agent.
2. the decoloring method of hexaphenoxycyclotriphosphazene according to claim 1, is characterized in that, the mass ratio of described gac and carclazyte is 1:1.
3. the decoloring method of hexaphenoxycyclotriphosphazene according to claim 1 and 2, it is characterized in that, for take phosphorus pentachloride, ammonium chloride, it is starting raw material, chlorobenzene is solvent, through the building-up reactions of too high selection, filter and obtain the chlorobenzene solution of highly purified hexachlorocyclotriphosphazene, then react in the process of preparing hexaphenoxycyclotriphosphazene with potassium phenylate, gac and carclazyte are added to as 15～20% of hexachlorocyclotriphosphazene crude product quality, bleaching temperature 70-85 ℃.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108690081A (en) * | 2018-05-22 | 2018-10-23 | 济南泰星精细化工有限公司 | A kind of preparation method of hexaphenoxycyclotriphosphazene |
| CN111848684A (en) * | 2020-08-11 | 2020-10-30 | 威海金威化学工业有限责任公司 | Method for separating mixed phenoxy phosphazene from hexaphenoxy cyclotriphosphazene crystallization mother liquor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108690081A (en) * | 2018-05-22 | 2018-10-23 | 济南泰星精细化工有限公司 | A kind of preparation method of hexaphenoxycyclotriphosphazene |
| CN111848684A (en) * | 2020-08-11 | 2020-10-30 | 威海金威化学工业有限责任公司 | Method for separating mixed phenoxy phosphazene from hexaphenoxy cyclotriphosphazene crystallization mother liquor |
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Application publication date: 20140122 |