CN102180908A - Method for preparing halogen-free high-efficiency flame retardant aryloxy cyclotriphosphazene compound - Google Patents
Method for preparing halogen-free high-efficiency flame retardant aryloxy cyclotriphosphazene compound Download PDFInfo
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Abstract
The invention discloses a method for preparing a halogen-free high-efficiency flame retardant aryloxy cyclotriphosphazene compound. The flame retardant is a pure white crystal product prepared by reacting sodium phenate and hexachlorocyclotriphosphazene serving as raw materials with dioxane serving as a solvent under heating and stirring, filtering and purifying. The preparation method of the flame retardant overcomes the defects of long reaction time, a yellow product color and high production cost existing in the conventional synthesis method commonly. The prepared flame retardant has the characteristics of high efficiency, no halogen, flame retardance, no toxicity, low smoke and the like, has high compatibility with most of organic polymer materials, and has processing stability and using stability.
Description
Technical field
The present invention relates to a kind of preparation method of fire retardant, specifically is a kind of preparation method of Halogen efficient flame-retarding agent aryloxy cyclotrinitrile phosphide.
Background technology
Low bromo etherate fire retardant, organism such as tetrabromodiphenyl ether, pentabromodiphenyl oxide, hexabromo phenyl ether, seven dibromodiphenyl ethers, octabromodiphenyl ether have persistency organic contaminant to environment, therefore are put in " Convention of Stockholm " appendix A to ban use of.Decabromodiphynly oxide is as one of broad-spectrum organic bromine flame retardant, widespread use in organic polymer materials such as polyolefine (PE, PP, ABS), polyester (PBT, PET), Resins, epoxy, fiber, although decabromodiphynly oxide is not directly listed in the forbidding scope of " Convention of Stockholm ", but the various low replacement bromo ether that it produces in production or degradation process, still there is the problem that causes the environmental persistence organic contamination, also thereby in succession forbidden by the laws and regulations of China and European Union.Therefore, once the flame retarded polymeric material field of widespread use decabromodiphynly oxide presses for alternative flame retardant products.At present, the developing direction of BACN is: have characteristics such as highly effective flame-retardant, nontoxic, low cigarette on flame retardant properties; Aspect processing Yu by the ignition resistant substrate material, have excellent compatibility and processing characteristics; In use do not move; Has excellent photostabilization; Aspect the ignition-proof element selection the halogen-free flameproof thing of compliance with environmental protection requirements such as reselection procedure phosphorus system, nitrogen system, silicon system.Use as fire retardant, its flame retarding efficiency height, anti-hydrolysis, anti-oxidant, living cigarette amount is low when burning or hot tearing, the low corrosion of degradation production, high low temperature use temperature wide ranges.
At present the synthetic method of the hexaphenoxycyclotriphosphazene (HPCTP) of report is mainly as follows: class methods are to react in tetrahydrofuran (THF) or toluene with highly basic such as sodium Metal 99.5, NaH or NaOH and phenol earlier to make anhydrous sodium phenylate, make HPCTP with hexachlorocyclotriphosphazene (HCCTP) reaction again, yield about 70%～95%, reaction times reaches 20～50 hours, and the use of sodium Metal 99.5, NaH causes reacting bad control; Another kind of method is that HCCTP, phenol, acid binding agent (salt of wormwood, triethylamine etc.) one are reacted in acetone solvent, product yield lower (being lower than 70%), solvent and acid binding agent consumption are big, the separating treatment trouble, or be raw material with HCCTP, phenol, NaOH, with the tetrabutylammonium chloride phase-transfer catalyst, chlorobenzene and water are solvent, synthetic HPCTP, the about yield 75% of productive rate.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of Halogen efficient flame-retarding agent aryloxy cyclotrinitrile phosphide, the preparation method of this kind fire retardant overcomes ubiquitous long reaction time in the existing synthetic method, product colour jaundice, the deficiency that production cost is high.The fire retardant of preparation has efficient halogen-free anti-inflaming, and is nontoxic, and characteristics such as low cigarette have good consistency, processing stability and stability in use with most organic polymer materials simultaneously.
Technical scheme of the present invention is: a kind of preparation method of Halogen efficient flame-retarding agent aryloxy cyclotrinitrile phosphide comprises the steps:
A. take by weighing raw material phenol sodium 12.0～17.9 by weight and hexachlorocyclotriphosphazene 4.5～6 is standby;
B. the dioxane that adds 90～120 weight parts in reaction vessel is dissolved in load weighted sodium phenylate and hexachlorocyclotriphosphazene in the dioxane as solvent, carries out the heated and stirred reaction, and temperature of reaction is 70～100 ℃, and the reaction times is 8～15 hours;
C. reaction product is cooled off and left standstill, the layering of question response product, the upper strata is a yellow solution, when lower floor is light yellow solid, remove by filter lower floor's solid, the yellow solution that filtration is obtained carries out the primary purification processing, obtain thick product, the thick product of gained is carried out the secondary purification processes, obtain the pure white crystal, be Halogen efficient flame-retarding agent aryloxy cyclotrinitrile phosphide.
Described primary purification treatment process is: with medium distilled water yellow solution is carried out crystallization and purification, drying obtains thick product white depositions.
Described secondary purification processing method is: thick product is carried out recrystallization with medium ethanol purify, drying obtains the pure white crystal.
The melting range of the Halogen efficient flame-retarding agent aryloxy cyclotrinitrile phosphide of the present invention's preparation is 110～114 ℃.
The invention has the beneficial effects as follows: among the present invention, the yield of aryloxy cyclotrinitrile phosphide reaches more than 85%, purity is greater than 99%, outward appearance is the pure white crystal, and solvent used in the preparation process is few, and safety and environmental protection, the easy commercial scale production of synthesis and preparation process, production cost is low, replacing or reducing brominated flame-retardant and fire retardant material, promotes fire retardant and fire retardant material to have great importance on developing to low-carbon high-efficiency, eco-friendly direction.
Aryloxy cyclotrinitrile phosphide is the efficient halogen-free anti-inflaming agent, does not contain halogens in the molecule, phosphorus, nitrogen element content height, a lot of organic polymers had the good flame effect, limiting oxygen index(LOI) LOI can be 30%～70%, and smoke density is low, satisfies the efficiently fire-retardant requirement of low cigarette environmental protection of Halogen.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to the following examples, embodiment should not regard the qualification to protection domain of the present invention as.
Embodiment 1
A. take by weighing raw material phenol sodium 12.5 by weight and hexachlorocyclotriphosphazene 5.0 is standby;
B. the dioxane that adds 100 weight parts in reaction vessel is dissolved in load weighted sodium phenylate and hexachlorocyclotriphosphazene in the dioxane as solvent, carries out the heated and stirred reaction, and temperature of reaction is 85 ℃, and the reaction times is 12.5 hours;
C. reaction product is cooled off and left standstill, the layering of question response product, the upper strata is a yellow solution, when lower floor is light yellow solid, remove by filter lower floor's solid, the yellow solution that filtration is obtained carries out primary purification and handles that (treatment process is: with medium distilled water yellow solution is carried out crystallization and purification, drying) obtains thick product, the thick product of gained is carried out the secondary purification processes, and (treatment process is: thick product is carried out recrystallization with medium ethanol purify, drying) obtains the pure white crystal, be Halogen efficient flame-retarding agent aryloxy cyclotrinitrile phosphide, yield is 85.6%.
Embodiment 2
A. take by weighing raw material phenol sodium 14 by weight and hexachlorocyclotriphosphazene 4.5 is standby;
B. the dioxane that adds 92 weight parts in reaction vessel is dissolved in load weighted sodium phenylate and hexachlorocyclotriphosphazene in the dioxane as solvent, carries out the heated and stirred reaction, and temperature of reaction is 75 ℃, and the reaction times is 14.5 hours;
C. reaction product is cooled off and left standstill, the layering of question response product, the upper strata is a yellow solution, when lower floor is light yellow solid, remove by filter lower floor's solid, the yellow solution that filtration is obtained carries out primary purification and handles that (treatment process is: with medium distilled water yellow solution is carried out crystallization and purification, drying) obtains thick product, the thick product of gained is carried out the secondary purification processes, and (treatment process is: thick product is carried out recrystallization with medium ethanol purify, drying) obtains the pure white crystal, be Halogen efficient flame-retarding agent aryloxy cyclotrinitrile phosphide, yield is 86.5%.
Embodiment 3
A. take by weighing raw material phenol sodium 16.0 by weight and hexachlorocyclotriphosphazene 5.5 is standby;
B. the dioxane that adds 118 weight parts in reaction vessel is dissolved in load weighted sodium phenylate and hexachlorocyclotriphosphazene in the dioxane as solvent, carries out the heated and stirred reaction, and temperature of reaction is 92 ℃, and the reaction times is 10 hours;
C. reaction product is cooled off and left standstill, the layering of question response product, the upper strata is a yellow solution, when lower floor is light yellow solid, remove by filter lower floor's solid, the yellow solution that filtration is obtained carries out primary purification and handles that (treatment process is: with medium distilled water yellow solution is carried out crystallization and purification, drying) obtains thick product, the thick product of gained is carried out the secondary purification processes, and (treatment process is: thick product is carried out recrystallization with medium ethanol purify, drying) obtains the pure white crystal, be Halogen efficient flame-retarding agent aryloxy cyclotrinitrile phosphide, yield is 88.0%.
Embodiment 4
A. take by weighing raw material phenol sodium 17.5 by weight and hexachlorocyclotriphosphazene 6.0 is standby;
B. the dioxane that adds 108 weight parts in reaction vessel is dissolved in load weighted sodium phenylate and hexachlorocyclotriphosphazene in the dioxane as solvent, carries out the heated and stirred reaction, and temperature of reaction is 98 ℃, and the reaction times is 8.5 hours;
C. reaction product is cooled off and left standstill, the layering of question response product, the upper strata is a yellow solution, when lower floor is light yellow solid, remove by filter lower floor's solid, the yellow solution that filtration is obtained carries out primary purification and handles that (treatment process is: with medium distilled water yellow solution is carried out crystallization and purification, drying) obtains thick product, the thick product of gained is carried out the secondary purification processes, and (treatment process is: thick product is carried out recrystallization with medium ethanol purify, drying) obtains the pure white crystal, be Halogen efficient flame-retarding agent aryloxy cyclotrinitrile phosphide, yield is 90.5%.
Claims (3)
1. the preparation method of a Halogen efficient flame-retarding agent aryloxy cyclotrinitrile phosphide is characterized in that, comprises the steps:
A. take by weighing raw material phenol sodium 12.0～17.9 by weight and hexachlorocyclotriphosphazene 4.5～6 is standby;
B. the dioxane that adds 90～120 weight parts in reaction vessel is dissolved in load weighted sodium phenylate and hexachlorocyclotriphosphazene in the dioxane as solvent, carries out the heated and stirred reaction, and temperature of reaction is 70～100 ℃, and the reaction times is 8～15 hours;
C. reaction product is cooled off and left standstill, the layering of question response product, the upper strata is a yellow solution, when lower floor is light yellow solid, remove by filter lower floor's solid, the yellow solution that filtration is obtained carries out the primary purification processing, obtain thick product, the thick product of gained is carried out the secondary purification processes, obtain the pure white crystal, be Halogen efficient flame-retarding agent aryloxy cyclotrinitrile phosphide.
2. the preparation method of a kind of Halogen efficient flame-retarding agent aryloxy cyclotrinitrile phosphide according to claim 1, it is characterized in that, the treatment process of primary purification described in the step c is: with medium distilled water yellow solution is carried out crystallization and purification, drying obtains thick product white depositions.
3. the preparation method of a kind of Halogen efficient flame-retarding agent aryloxy cyclotrinitrile phosphide according to claim 1, it is characterized in that, secondary purification processing method described in the step c is: thick product is carried out recrystallization with medium ethanol purify, drying obtains the pure white crystal.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333344A (en) * | 2013-06-06 | 2013-10-02 | 西安近代化学研究所 | Method for purifying aryloxy polyphosphazene |
| CN103435654A (en) * | 2013-09-03 | 2013-12-11 | 张家港市信谊化工有限公司 | Preparation method of hexaphenoxy cyclotriphosphazene |
| CN103435653A (en) * | 2013-08-08 | 2013-12-11 | 清远市普塞呋磷化学有限公司 | Preparation method of hexaphenoxycyclotriphosphazene (HPCTP) |
| CN103524563A (en) * | 2013-10-30 | 2014-01-22 | 威海金威化学工业有限责任公司 | Hexaphenoxy cyclotriphosphazene decolorizing method |
| 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 |
| CN106336435A (en) * | 2016-08-25 | 2017-01-18 | 威海金威化学工业有限责任公司 | Improved hexaphenoxycyclotriphosphazene preparation method |
| CN106518928A (en) * | 2016-10-27 | 2017-03-22 | 湖南师范大学 | A synthetic method of alkoxy(pentafluoro) or phenoxyl(pentafluoro) cyclotriphosphazene |
| CN110157072A (en) * | 2019-05-22 | 2019-08-23 | 东莞华尔泰装饰材料有限公司 | A kind of fireproof aluminum-plastic board containing nano-meter flame retardants and its dedicated core material |
| CN113024605A (en) * | 2019-12-24 | 2021-06-25 | 中蓝晨光化工研究设计院有限公司 | Synthesis method of hexaphenoxycyclotriphosphazene flame retardant |
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| CN1284508A (en) * | 2000-09-07 | 2001-02-21 | 中国科学院兰州化学物理研究所 | Synthesis process of aryloxy cyclotrinitrile phosphide |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103333344A (en) * | 2013-06-06 | 2013-10-02 | 西安近代化学研究所 | Method for purifying aryloxy polyphosphazene |
| CN103333344B (en) * | 2013-06-06 | 2015-08-12 | 西安近代化学研究所 | A kind of purification process of aryloxy polyphosphazene |
| CN103435653A (en) * | 2013-08-08 | 2013-12-11 | 清远市普塞呋磷化学有限公司 | Preparation method of hexaphenoxycyclotriphosphazene (HPCTP) |
| CN103435653B (en) * | 2013-08-08 | 2015-12-02 | 清远市普塞呋磷化学有限公司 | A kind of preparation method of hexaphenoxycyclotriphosphazene |
| CN103435654A (en) * | 2013-09-03 | 2013-12-11 | 张家港市信谊化工有限公司 | Preparation method of hexaphenoxy cyclotriphosphazene |
| CN103435654B (en) * | 2013-09-03 | 2016-05-11 | 张家港市信谊化工有限公司 | A kind of preparation method of hexaphenoxycyclotriphosphazene |
| CN103524563A (en) * | 2013-10-30 | 2014-01-22 | 威海金威化学工业有限责任公司 | Hexaphenoxy cyclotriphosphazene decolorizing method |
| 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 |
| CN106336435A (en) * | 2016-08-25 | 2017-01-18 | 威海金威化学工业有限责任公司 | Improved hexaphenoxycyclotriphosphazene preparation method |
| CN106518928A (en) * | 2016-10-27 | 2017-03-22 | 湖南师范大学 | A synthetic method of alkoxy(pentafluoro) or phenoxyl(pentafluoro) cyclotriphosphazene |
| CN110157072A (en) * | 2019-05-22 | 2019-08-23 | 东莞华尔泰装饰材料有限公司 | A kind of fireproof aluminum-plastic board containing nano-meter flame retardants and its dedicated core material |
| CN113024605A (en) * | 2019-12-24 | 2021-06-25 | 中蓝晨光化工研究设计院有限公司 | Synthesis method of hexaphenoxycyclotriphosphazene flame retardant |
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