CN103570763A - Novel method for synthesizing and purifying phosphonitrilic chloride trimer - Google Patents
Novel method for synthesizing and purifying phosphonitrilic chloride trimer Download PDFInfo
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- CN103570763A CN103570763A CN201210254611.XA CN201210254611A CN103570763A CN 103570763 A CN103570763 A CN 103570763A CN 201210254611 A CN201210254611 A CN 201210254611A CN 103570763 A CN103570763 A CN 103570763A
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- Prior art keywords
- chlorobenzene
- ammonium chloride
- purifying
- lewis acid
- hexa chloro
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Abstract
The invention discloses a novel method for synthesizing and purifying phosphonitrilic chloride trimer by taking Lewis acid as the catalyst and adopting the sublimation method. The method disclosed by the invention is characterized by comprising the following steps of: synthesizing phosphonitrilic chloride trimer in chlorobenzene as the solvent by selecting Lewis acid as the catalyst and taking ammonium chloride and phosphorus pentachloride as the raw materials, after removing chlorobenzene, dissolving phosphonitrilic chloride trimer by using normal hexane to eliminate linear polymer, and finally, purifying by adopting the sublimation method to obtain phosphonitrilic chloride trimer with the purity of above 99%, wherein the total yield is about 60%. Compared with the prior art, the catalytic system is optimized; the purity of the prepared phosphonitrilic chloride trimer is high; and the novel method disclosed by the invention is applied to industrialized mass production.
Description
Technical field
The present invention relates to a kind of novel method of preparing purifying fine-chemical intermediate, particularly relate to a kind of novel method of synthesizing and purifying hexa chloro cyclotripolyphosphazene, belong to chemical industry synthesizing and purifying field.
Background technology
Phosphazene compound be a class skeleton by the inorganic-organic compound of phosphorus atom and nitrogen-atoms alternative arrangement, can be divided into ring phosphonitrile and polyphosphonitrile.Cyclic phosphazene compound be a class to take the polynary ring of phosphorus nitrogen-atoms alternative arrangement be skeleton, the class inorganics forming by two substituting groups that change on phosphorus atom.Its material qualitative diversity after polymerization is given in the variation of phosphazene compound Side base, as good flame retardant resistance, high temperature resistant, anti-oxidant and organic solvent-resistant etc.At aspects such as material fuel batteries, there is good purposes.Therefore, having development and application values widely, is one of the most rising inorganic macromolecule material.
Hexachlorocyclotriphosphazene is the phosphazene compound obtaining the earliest, and the chlorine on its phosphorus atom is very active, easily by various affinity reagent, is replaced and obtains various not isoplastic cyclic phosphazene compounds.Hexa chloro cyclotripolyphosphazene is the most basic compound in phosphonitrile chemistry, to the development of phosphonitrile chemistry, plays a part very important.
Publication number is traditional preparation method that the patent of US4567028 and CN101157704A discloses hexachlorocyclotriphosphazene, is with PCl
5and NH
4cl is raw material, the pyridine etc. of take is catalyzer, certain hour refluxes in inert solvent, then steam except chlorobenzene, recrystallization obtains product, but in fact adopting pyridine is the recycling that catalyzer is unfavorable for chlorobenzene, and recrystallization cannot remove the cyclic tetramer in system completely, can not get highly purified product.Also have the patent that publication number is US4605539 to adopt washing to remove cyclic tetramer, but to cyclic trimer, also can damage simultaneously, cannot obtain the product that purity is high, yield is also affected.The making method that these are traditional, yield is low, and product purity is low, and cost is high, is not suitable for industrialized production.Therefore, find a technique economical and practical and applicable industrialized production extremely urgent.
Summary of the invention
The object of the invention is the operational path that finds can be applicable to industrialized production, improve the yield of hexa chloro cyclotripolyphosphazene, reduce costs, obtain highly purified hexa chloro cyclotripolyphosphazene product.
The invention provides one can the highly purified hexa chloro cyclotripolyphosphazene of industrialized production novel method, step comprises:
Step 1, in reaction flask, adds appropriate ammonium chloride as reaction medium, take ammonium chloride and phosphorus pentachloride as raw material, and adds a certain amount of Lewis acid as catalyzer, at a certain temperature reacting by heating certain hour;
Step 2, normal pressure evaporates part chlorobenzene, is cooled to 40-50
oafter C, remove by filter unnecessary ammonium chloride, then decompression removes remaining chlorobenzene, be cooled to after room temperature, add n-hexane dissolution hexa chloro cyclotripolyphosphazene, filter to remove linear polymer, decompression is removed hexane solution and is obtained the thick product of hexa chloro cyclotripolyphosphazene.
Step 3, adopts subliming method purifying, obtains purity and reaches more than 99% hexa chloro cyclotripolyphosphazene.
Method as mentioned above, wherein, used catalyst Lewis acid comprises ZnCl
2,feCl
3,alCl
3,coCl
2,mnCl
2,mgCl
2deng.
Method as mentioned above, wherein, temperature of reaction is 100
oc-130
oc, the reaction times is 8-16 hour.
Method as mentioned above, wherein, the consumption of ammonium chloride is 150-160%, the consumption of catalyzer Lewis acid is 0.5-0.6%.
Method as mentioned above, wherein, preferred ZnCl
2for catalyzer.
Method as mentioned above, wherein, preferable reaction temperature is 128
oc.
Method as mentioned above, wherein, the more than 99% hexa chloro cyclotripolyphosphazene yield obtaining is 60%.
In sum, the present invention has been owing to having adopted technique scheme, makes chlorobenzene and the normal hexane can recycling, improved the yield of hexa chloro cyclotripolyphosphazene, reduced cost, obtained highly purified hexa chloro cyclotripolyphosphazene product, economical and practical and applicable industrialized production.
Embodiment
Below by embodiment, specifically describe the present invention, but embodiment does not limit the scope of the invention.
Embodiment 1:
In tri-mouthfuls of reaction flasks of 500 mL, add the ammonium chloride of 20 g, 300 mL chlorobenzenes and 50.8 g phosphorus pentachlorides, and add 0.4 g FeCl
3catalyzer, react on 125
oc thermotonus 8 hours, normal pressure evaporates part chlorobenzene, is cooled to 40-50
oc removes by filter unnecessary ammonium chloride, then decompression removes remaining chlorobenzene, is cooled to room temperature, adds n-hexane dissolution product to filter to remove linear polymer, and decompression is removed hexane solution and obtained the thick product of hexa chloro cyclotripolyphosphazene.By sublimation purification, obtain more than 99% hexa chloro cyclotripolyphosphazene 10 g, yield 35%.
Embodiment 2:
In tri-mouthfuls of reaction flasks of 500 mL, add the ammonium chloride of 20 g, 300 mL chlorobenzenes and 50.8 g phosphorus pentachlorides, and add 0.4 g AlCl
3catalyzer, react on 125
oc thermotonus 8 hours, normal pressure evaporates part chlorobenzene, is cooled to 40-50
oc removes by filter unnecessary ammonium chloride, then decompression removes remaining chlorobenzene, is cooled to room temperature, adds n-hexane dissolution product to filter to remove linear polymer, and decompression is removed hexane solution and obtained the thick product of hexa chloro cyclotripolyphosphazene.By sublimation purification, obtain more than 99% hexa chloro cyclotripolyphosphazene 12 g, yield 42%.Embodiment 3:
In tri-mouthfuls of reaction flasks of 5 L, add the ammonium chloride of 200 g, 3000 mL chlorobenzenes and 500 g phosphorus pentachlorides, and add 2.0 g ZnCl
2catalyzer, react on 128
oc thermotonus 15 hours, normal pressure evaporates part chlorobenzene, is cooled to 40-50
oc removes by filter unnecessary ammonium chloride, then decompression removes remaining chlorobenzene, is cooled to room temperature, adds n-hexane dissolution product to filter to remove linear polymer, and decompression is removed hexane solution and obtained the thick product of hexa chloro cyclotripolyphosphazene.By sublimation purification, obtain more than 99% hexa chloro cyclotripolyphosphazene 166 g, yield 60%.
Embodiment 4:
In tri-mouthfuls of reaction flasks of 5 L, add the ammonium chloride of 200 g, 3000 mL chlorobenzenes (embodiment 2 reclaims chlorobenzene) and 500 g phosphorus pentachlorides, and add 2.0 g ZnCl
2catalyzer, react on 128
oc thermotonus 15 hours, normal pressure evaporates part chlorobenzene, is cooled to temperature 40-50
oc removes by filter unnecessary ammonium chloride, then decompression removes remaining chlorobenzene, is cooled to room temperature, adds normal hexane (embodiment 2 reclaim normal hexanes) dissolved product to filter to remove linear polymer, and decompression is removed hexane solution and obtained the thick product of hexa chloro cyclotripolyphosphazene.By sublimation purification, obtain more than 99% hexa chloro cyclotripolyphosphazene 164 g, yield 58%.
Above specific embodiments of the invention be have been described in detail, but it is just as example, the present invention is not restricted to specific embodiment described above.To those skilled in the art, any equivalent modifications that the present invention is carried out and alternative also all among category of the present invention.Therefore, equalization conversion and the modification done without departing from the spirit and scope of the invention, all should contain within the scope of the invention.
Claims (7)
1. a novel method for synthesizing and purifying hexa chloro cyclotripolyphosphazene, is characterized in that, step comprises:
Step 1, take ammonium chloride and phosphorus pentachloride as raw material, take Lewis acid as catalyzer, at a certain temperature reacting by heating certain hour in chlorobenzene medium;
Step 2, removes after chlorobenzene and unnecessary ammonium chloride, with n-hexane dissolution hexa chloro cyclotripolyphosphazene, removes linear polymer, and decompression is removed hexane solution and obtained the thick product of hexa chloro cyclotripolyphosphazene;
Step 3, adopts subliming method purifying, obtains purity and reaches more than 99% hexa chloro cyclotripolyphosphazene.
2. method according to claim 1, is characterized in that, used catalyst Lewis acid comprises ZnCl
2,feCl
3,alCl
3,coCl
2,mnCl
2,mgCl
2deng.
3. method according to claim 1, is characterized in that, temperature of reaction is 100
oc-130
oc, the reaction times is 8-16 hour.
4. method according to claim 1, is characterized in that, the consumption of ammonium chloride is 150-160%, and the consumption of catalyzer Lewis acid is 0.5-0.6%.
5. method according to claim 1, is characterized in that, the method for removing chlorobenzene and unnecessary ammonium chloride is: normal pressure evaporates part chlorobenzene, is cooled to 40-50
oafter C, remove by filter unnecessary ammonium chloride, then decompression remove remaining chlorobenzene, be then cooled to room temperature.
6. Lewis acid according to claim 2, is characterized in that ZnCl
2for catalyzer.
7. temperature of reaction according to claim 3, is characterized in that, temperature of reaction is 128
oc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210254611.XA CN103570763A (en) | 2012-07-23 | 2012-07-23 | Novel method for synthesizing and purifying phosphonitrilic chloride trimer |
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|---|---|---|---|
| CN201210254611.XA CN103570763A (en) | 2012-07-23 | 2012-07-23 | Novel method for synthesizing and purifying phosphonitrilic chloride trimer |
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|---|---|
| CN103570763A true CN103570763A (en) | 2014-02-12 |
Family
ID=50043539
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|---|---|---|---|
| CN201210254611.XA Pending CN103570763A (en) | 2012-07-23 | 2012-07-23 | Novel method for synthesizing and purifying phosphonitrilic chloride trimer |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558044A (en) * | 2015-02-13 | 2015-04-29 | 湖北诺邦科技股份有限公司 | Synthesis method of hexachlorocyclotriphosphazene |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4382914A (en) * | 1980-06-11 | 1983-05-10 | Nippon Fine Chemical Company, Ltd. | Process for preparing cyclic phosphonitrilic chloride oligomers |
| CN1850832A (en) * | 2006-05-23 | 2006-10-25 | 郑州大学 | Catalytic synthesizing method of hexa chloro cyclotripolyphosphazene |
| CN1916007A (en) * | 2006-09-13 | 2007-02-21 | 上海氯碱化工股份有限公司 | Preparing hexachlorocyclotriphosphazene, and purification method |
| CN101157704A (en) * | 2007-11-08 | 2008-04-09 | 河北大学 | Method for micro-wave synthesis of hexachloride ring polyphosphazenes |
| CN101602780A (en) * | 2009-06-26 | 2009-12-16 | 四川东材科技集团股份有限公司 | The process for catalytic synthesis of hexachlorocyclotriphosphazene |
| CN102070672A (en) * | 2011-01-18 | 2011-05-25 | 宁波职业技术学院 | Method for preparing hexachlorocyclotriphosphazene |
-
2012
- 2012-07-23 CN CN201210254611.XA patent/CN103570763A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4382914A (en) * | 1980-06-11 | 1983-05-10 | Nippon Fine Chemical Company, Ltd. | Process for preparing cyclic phosphonitrilic chloride oligomers |
| CN1850832A (en) * | 2006-05-23 | 2006-10-25 | 郑州大学 | Catalytic synthesizing method of hexa chloro cyclotripolyphosphazene |
| CN1916007A (en) * | 2006-09-13 | 2007-02-21 | 上海氯碱化工股份有限公司 | Preparing hexachlorocyclotriphosphazene, and purification method |
| CN101157704A (en) * | 2007-11-08 | 2008-04-09 | 河北大学 | Method for micro-wave synthesis of hexachloride ring polyphosphazenes |
| CN101602780A (en) * | 2009-06-26 | 2009-12-16 | 四川东材科技集团股份有限公司 | The process for catalytic synthesis of hexachlorocyclotriphosphazene |
| CN102070672A (en) * | 2011-01-18 | 2011-05-25 | 宁波职业技术学院 | Method for preparing hexachlorocyclotriphosphazene |
Non-Patent Citations (3)
| Title |
|---|
| 张亨: "我国六氯环三磷腈的合成和应用研究进展", 《塑料助剂》 * |
| 张长水等: "六氯环三磷腈的催化合成与表征", 《河南师范大学学报(自然科学版)》 * |
| 简海峰等: "六氯环三磷腈的制备研究", 《化工科技》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104558044A (en) * | 2015-02-13 | 2015-04-29 | 湖北诺邦科技股份有限公司 | Synthesis method of hexachlorocyclotriphosphazene |
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Application publication date: 20140212 |