CN101735827B - Halogen-free aryl phosphonitrile fire retardant and preparation method thereof - Google Patents
Halogen-free aryl phosphonitrile fire retardant and preparation method thereof Download PDFInfo
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- CN101735827B CN101735827B CN 200910273060 CN200910273060A CN101735827B CN 101735827 B CN101735827 B CN 101735827B CN 200910273060 CN200910273060 CN 200910273060 CN 200910273060 A CN200910273060 A CN 200910273060A CN 101735827 B CN101735827 B CN 101735827B
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Abstract
The invention relates to a halogen-free aryl phosphonitrile fire retardant and a preparation method thereof. The preparation method comprises: reacting phosphorus pentachloride, ammonium chloride, a complexing agent, chlorobenzene and a metal chloride catalyst for 4-5 hours at a reflux temperature, filtering a solution, removing the excessive ammonium chloride, adding the filtrate to a reaction kettle, adding sodium salt or potassium salt of aryl or combination thereof, uniformly agitating, heating, refluxing and reacting for 3-10 hours, filtering a reaction mixture, taking the filtrate part, depressurizing and distilling to remove solvent, adding ethanol to residue for washing, filtering and drying to obtain the halogen-free aryl phosphonitrile fire retardant. The preparation method of the invention is simple, greatly simplifies operation steps. The first step of the reaction saves water washing and recrystallization, so as to avoid the generation of lots of waste water, save cost and protect environment. The side product for synthesizing hexachlorocyclotriphosphazene is directly used so as to greatly improve yield and the utilization rate of resources. The aryloxyl cyclotetraphosphonitrile and the aryloxyl phosphonitrile oligomer in the products greatly improve the solubility of the products in the solvent and are convenient for application.
Description
Technical field
The present invention relates to fire retardant material of a kind of halogen-free aryl phosphonitrile and preparation method thereof.
Background technology
Phosphorus, nitrogen compound are studied widely and are used as the fire retardant with environmental protection characteristic.In the molecule of cyclic phosphazene compound, contain two commutable active chlorine atoms on the phosphorus atom, can obtain multiple derivative by various substitution reactions, phosphazene derivative has higher phosphorus, nitrogen content, no matter this has just determined it is as flame retardant type functional materials or the flame-retardant additive of various materials, all have good flame retardant resistance and thermotolerance.Developed country is researching and developing phosphonitrile compounds fire retardant in recent decades always.Although the polymkeric substance of ring phosphonitrile---polyphosphonitrile have water-fast, anti-solvent, oil resistant class and chemical, radiation hardness, high temperature resistant and low temperature resistant, do not burn and the premium properties such as fire-retardant, the synthetic method of polyphosphonitrile does not obtain important breakthrough always, so up to the present, phosphazene flame retardant mainly concentrates on ring three phosphazene derivatives.Its preparation process mainly is to prepare first to purify to obtain hexachlorocyclotriphosphazene, further prepares the aryl cyclotrinitrile phosphide with the reaction such as substituted phenol again.Therefore hexachlorocyclotriphosphazene is the critical materials of phosphonitrile class bittern-free flame-proof material.
But up to the present, prepare hexachlorocyclotriphosphazene although proposed several different methods.But high yield, pollution-free preparation hexachlorocyclotriphosphazene still fail to realize industrial-scale production.Major cause be the preparation hexachlorocyclotriphosphazene process in except primary product, there are the by products such as a large amount of ring four phosphonitriles, phosphonitrile oligomer to produce, and these by products are studied at present fully, all by the mode of washing and recrystallization it are removed as by product.If industrial production is not only brought a large amount of waste water, and greatly waste resource; Simultaneously hexachlorocyclotriphosphazene production also produces other a large amount of by products, example hydrochloric acid etc., these drawbacks limit being widely used of phosphazene flame retardant.
Summary of the invention
The technical problem to be solved in the present invention is that to overcome existing hexachlorocyclotriphosphazene technology of preparing productive rate lower, a large amount of by products are removed, raw material can not obtain from a minute utilization, and produce the shortcoming of the pollutents such as a large amount of waste water, spent acid, provide a kind of cleaning to prepare halogen-free aryl phosphonitrile fire retardant and Preparation Method thereof.The method is take phosphorus pentachloride and ammonium chloride as raw material, and preparation contains the composition of hexachlorocyclotriphosphazene, ring four phosphonitriles, oligomeric phosphonitrile, without separating-purifying directly with the aryl compound reaction that contains special groups, directly prepare halogen-free aryl phosphonitrile fire retardant.
The object of the present invention is achieved like this: a kind of halogen-free aryl phosphonitrile fire retardant, and its component is by weight percentage:
Aryl rings three phosphonitriles 50～100%
Aryl rings four phosphonitriles 0～40%
The oligomeric phosphonitrile 0～15% of aryl
Said aryl is that general structure is-X-C
6H
4A kind of or its composition of-R, the symbol definition in the general formula is: X is O, S or NY; Y be H ,-C
6H
4-R or C
1To C
7Alkane;
R be H ,-CH
3,-CH
2OH ,-CHO ,-COOCH
3,-COOCH
2CH
3,-COCH
3,-CN ,-Ph or-NO
2
A kind of method for preparing halogen-free aryl phosphonitrile fire retardant,
(1), the phosphorus pentachloride, ammonium chloride, complexing agent, chlorobenzene and the metal chloride catalyst that in reactor, add metering under reflux temperature, react usefulness acid absorption tower absorption tail gas hydrogenchloride in the reaction process 4-5 hour;
(2), with the solution filter of step (1), remove the excess chlorination ammonium, filtrate adds in the reactor, and to the aryl of the said structure general formula that wherein adds a kind of metering or sodium salt or the sylvite of its composition, the post-heating back flow reaction that stirs 3-10 hour, react complete after, filter reaction mixture, get the filtrate part, the underpressure distillation desolventizing, in residue, add washing with alcohol, get halogen-free aryl phosphonitrile fire retardant behind the filtration drying;
The mol ratio of phosphorus pentachloride and ammonium chloride is 1: 1.1-1.3;
The mol ratio of catalyzer and phosphorus pentachloride is 1: 0.001-0.01;
The mol ratio of complexing agent and phosphorus pentachloride is 1: 0.024-0.03;
The mol ratio of phosphorus pentachloride and aryl salt is 1: 2.1-3.0;
In the chlorobenzene, the total weight concentration of each component is 20-45%.
Described complexing agent adopts pyridine or triethylamine.
Described metal chloride catalyst is selected from magnesium chloride, aluminum chloride, zinc chloride or its composition.
Halogen-free aryl phosphonitrile fire retardant provided by the invention and preparation method thereof has following effective effect:
1, the preparation method simply, has greatly simplified operation steps; 2, the reaction the first step is saved washing and recrystallization, has avoided the generation of a large amount of waste water, saves cost and protection of the environment; The by product that 3, will synthesize hexachlorocyclotriphosphazene directly utilizes, and has greatly improved productive rate, has improved resource utilization; 4, aryloxy ring four phosphonitriles in the product and the oligomeric phosphonitrile of aryloxy have increased the solubleness of product in solvent, are convenient to use.
Embodiment
Embodiment 1:
In the there-necked flask of 2L, add 98g ammonium chloride, the 600mL chlorobenzene, 1.5g zinc chloride and 2mL pyridine, open and stir, under reflux state, drip the chlorobenzene solution (needing chlorobenzene 800mL) be dissolved with the 298g phosphorus pentachloride, added in 2-3 hour, 132 ℃ of stopped heatings when HCl obviously weakened to the airway in 2～3 hours that reflux.After reaction finished, cooling reaction system filtered, and gets yellow solution.Solution is joined in the there-necked flask of 2L, add again 349g phenol sodium salt, heated and stirred back flow reaction 6 hours.Cooling, filter, filtrate is carried out underpressure distillation, reclaim the solvent chlorobenzene, in resultant product, add hot ethanol, washing, suction filtration, the dry phenoxy phosphazene product 304g that gets, productive rate 92%, wherein phenoxy cyclotriphosphazene content is 92.1%, and phenoxy group ring four phosphonitriles are 4.7%, the oligomeric phosphonitrile 3.2% of phenoxy group.105-113 ℃ of product melting range.
Embodiment 2:
In the glass reaction still of 20L, add 2kg ammonium chloride, the 6L chlorobenzene, 40g zinc chloride and 40mL pyridine, open and stir, under reflux state, drip the chlorobenzene solution (needing chlorobenzene 6L) be dissolved with the 6kg phosphorus pentachloride, added in 2-3 hour, make solution stopped heating when HCl obviously weakened to the airway in 3～4 hours that continues to keep refluxing.After reaction finished, cooling reaction system filtered, and gets yellow solution.Solution is joined in the reactor again, add again 7.03kg phenol sodium salt, heated and stirred back flow reaction 6 hours.Cooling, filter, filtrate is carried out underpressure distillation, reclaim the solvent chlorobenzene, in resultant product, add hot ethanol, washing, suction filtration, the dry phenoxy phosphazene product 6.25kg that gets, productive rate 94%, wherein phenoxy cyclotriphosphazene content is 87.7%, and phenoxy group ring four phosphonitriles are 8.8%, the oligomeric phosphonitrile 3.5% of phenoxy group.80-110 ℃ of product melting range.
Embodiment 3:
In the enamel reaction still of 2000L, add 200kg ammonium chloride, the 500L chlorobenzene, 7.5kg zinc chloride and 800mL pyridine, open and stir, under reflux state, add the chlorobenzene solution (needing chlorobenzene 600L) be dissolved with the 600kg phosphorus pentachloride, added in 3-4 hour, make solution stopped heating when HCl obviously weakened to the airway in 3～5 hours that continues to keep refluxing.After reaction finished, cooling reaction system filtered, and gets yellow solution.Solution is joined in the reactor again, add again 706kg phenol sodium salt, heated and stirred back flow reaction 6 hours.Cooling, filter, filtrate is carried out underpressure distillation, reclaim the solvent chlorobenzene, in resultant product, add hot ethanol, washing, suction filtration, the dry phenoxy phosphazene product 632kg that gets, productive rate 95%, wherein phenoxy cyclotriphosphazene content is 76.9%, and phenoxy group ring four phosphonitriles are 14.6%, the oligomeric phosphonitrile 8.5% of phenoxy group.70-100 ℃ of product melting range.
In above embodiment, the complexing agent pyridine also can adopt triethylamine.Zinc chloride turns to a kind of in the metal chloride catalyst, and chlorine magnesium chloride, aluminum chloride, zinc chloride or its composition also can be used as metal chloride catalyst and use in the present invention.
By the halogen-free aryl phosphonitrile fire retardant that above method obtains, by weight percentage, it consists of:
Aryl rings three phosphonitriles 50～100%
Aryl rings four phosphonitriles 0～40%
The oligomeric phosphonitrile 0～15% of aryl
Aryl is that general structure is-X-C
6H
4A kind of or its composition of-R, the symbol definition in the general formula is: X is O, S or NY; Y be H ,-C
6H
4-R or C
1To C
7Alkane;
R be H ,-CH
3,-CH
2OH ,-CHO ,-COOCH
3,-COOCH
2CH
3,-COCH
3,-CN ,-Ph or-NO
2
Claims (3)
1. the preparation method of a halogen-free aryl phosphonitrile fire retardant is characterized in that: may further comprise the steps:
(1), the phosphorus pentachloride, ammonium chloride, complexing agent, chlorobenzene and the metal chloride catalyst that in reactor, add metering under reflux temperature, react usefulness acid absorption tower absorption tail gas hydrogenchloride in the reaction process 4-5 hour;
(2), with the solution filter of step (1), remove the excess chlorination ammonium, filtrate adds in the reactor, and to the aryl of the following general structural formula that wherein adds a kind of metering or sodium salt or the sylvite of its composition, the post-heating back flow reaction that stirs 3-10 hour, react complete after, filter reaction mixture, get the filtrate part, the underpressure distillation desolventizing, in residue, add washing with alcohol, get halogen-free aryl phosphonitrile fire retardant behind the filtration drying;
The mol ratio of phosphorus pentachloride and ammonium chloride is 1:1.1-1.3;
The mol ratio of catalyzer and phosphorus pentachloride is 1:0.001-0.01;
The mol ratio of complexing agent and phosphorus pentachloride is 1:0.024-0.03;
The mol ratio of phosphorus pentachloride and aryl salt is 1:2.1-3.0;
In the chlorobenzene, the total weight concentration of each component is 20-45%;
The component of resulting halogen-free aryl phosphonitrile fire retardant is by weight percentage:
Aryl rings three phosphonitriles 50 ~ 100%
Aryl rings four phosphonitriles 0 ~ 40%
The oligomeric phosphonitrile 0 ~ 15% of aryl
Said aryl is that general structure is-X-C
6H
4A kind of or its composition of-R, the symbol definition in the general formula is: X is O or S; R be H ,-CH
3,-CH
2OH ,-CHO ,-COOCH
3,-COOCH
2CH
3,-COCH
3,-CN ,-Ph or-NO
2
2. the method for preparing halogen-free aryl phosphonitrile fire retardant according to claim 1 is characterized in that: described complexing agent employing pyridine or triethylamine.
3. the method for preparing halogen-free aryl phosphonitrile fire retardant according to claim 1, it is characterized in that: described metal chloride catalyst is selected from magnesium chloride, aluminum chloride, zinc chloride or its composition.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102070672B (en) * | 2011-01-18 | 2013-02-06 | 宁波职业技术学院 | Method for preparing hexachlorocyclotriphosphazene |
| CN103351468B (en) * | 2013-06-06 | 2015-08-26 | 西安近代化学研究所 | A kind of purification process of aryloxy polyphosphazene |
| CN103554550B (en) * | 2013-10-30 | 2015-01-14 | 威海金威化学工业有限责任公司 | Utilization method of byproduct in synthetic process of phosphonitrilic chloride trimer |
| CN113651854B (en) * | 2021-08-13 | 2022-12-23 | 青岛科技大学 | Phosphazene compound and preparation method and application thereof |
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| CN101407527A (en) * | 2008-04-17 | 2009-04-15 | 苏州大学 | Fluoride alkoxycyclotriphosphazene derivative, preparation and use thereof |
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2009
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| US7511383B2 (en) * | 2005-04-04 | 2009-03-31 | Shin-Etsu Chemical Co., Ltd. | Flame retardant and an epoxy resin composition comprising the same for encapsulating semiconductor devices |
| CN101012242A (en) * | 2007-01-26 | 2007-08-08 | 华中科技大学 | Cyclophosphaxene compound as flame-proof material and synthetic method thereof |
| CN101407527A (en) * | 2008-04-17 | 2009-04-15 | 苏州大学 | Fluoride alkoxycyclotriphosphazene derivative, preparation and use thereof |
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