CN102702268A - Preparation method of pentafluoroalkoxy or phenoxy cyclotriphosphazene - Google Patents
Preparation method of pentafluoroalkoxy or phenoxy cyclotriphosphazene Download PDFInfo
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- CN102702268A CN102702268A CN2012101639348A CN201210163934A CN102702268A CN 102702268 A CN102702268 A CN 102702268A CN 2012101639348 A CN2012101639348 A CN 2012101639348A CN 201210163934 A CN201210163934 A CN 201210163934A CN 102702268 A CN102702268 A CN 102702268A
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- fluoroalkyloxies
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Abstract
The invention relates to a preparation method of pentafluoroalkoxy or phenoxy cyclotriphosphazene. The preparation method comprises the steps of taking hexachlorocyclotriphosphazene as raw material, using the nucleophilic reagent alkoxide (or phenoxide) to substitute one chloride atom on the hexachlorocyclotriphosphazene to obtain pentachloro alkoxy (or phenoxy) cyclotriphosphazene, and then performing fluoridation with the fluorinating agent. According to the preparation method, the process is simple and harmful substance can not be generated.
Description
Technical field
The present invention relates to a kind of method for making of phosphazene derivative, the preparation method of particularly a kind of five Fluoroalkyloxies or phenoxy ring three phosphonitriles.
Background technology
Phosphonitrile can be used for preparing high temperature resistant, low temperature resistant, oxidation resistant military affairs and aerospace industry self-extinguishing fire retardant, biomedical material and the medicinal slow release agent with specialty elastomer and resilient material, plastics, fiber etc.; Gather the organophosphorus nitrile compound simultaneously and also be applied to mould material, macromolecule conductor, high molecule liquid crystal, optical material, polymeric dielectrics, polymer catalyst etc.; Phosphazene derivative also can be used as the lithium-ion battery electrolytes fire retardant.
Many pieces of patents disclosed all is to be the preparation method of five Fluoroalkyloxy rings, three phosphonitriles of raw material with the hexachlorocyclotriphosphazene for U.S. Pat 2004191635, Japanese Patent JP2009161559, Chinese patent ZL200810023746.9 etc.; Promptly earlier hexachlorocyclotriphosphazene is made hexafluoro ring three phosphonitriles through fluoridizing, then hexafluoro ring three phosphonitriles and alkoxyl group alkoxide, phenoxy alkoxide react the method that makes phosphazene derivative; This method has deleterious fluorochemical and produces at hexafluoro ring three phosphonitriles and alkoxyl group alkoxide, when the phenoxy alkoxide reacts and makes phosphazene derivative.
Summary of the invention
In order to overcome above-mentioned shortcoming, the invention provides a kind of is raw material with the hexachlorocyclotriphosphazene, adopts first alcoxyl (or benzene) baseization, the preparation method of back fluorizated phosphazene derivative.
The present invention is achieved in that the preparation method of a kind of five Fluoroalkyloxies or phenoxy ring three phosphonitriles; It is characterized in that: a chlorine atom that in organic solvent, replaces on the hexachlorocyclotriphosphazene with nucleophilic reagent alkoxide or phenates earlier obtains pentachloro-alkoxyl group or phenoxy ring three phosphonitriles, then carries out five Fluoroalkyloxies or phenoxy ring three phosphonitriles of fluoridation with fluorizating agent.
Said hexachlorocyclotriphosphazene product reacts with alkoxide or phenates in organic solvent, makes to contain pentachloro-alkoxyl group or phenoxy ring three phosphonitrile products; Then it is distilled, distillate by product and solvent after, obtain pentachloro-alkoxyl group or phenoxy ring three phosphonitriles; The temperature of above-mentioned reaction is 30～90 ℃, and 50～80 ℃ better; Reaction times is 3～10 hours, and 5～8 hours better.
The used alcohols (or phenol) of above-mentioned reaction can be any in ethanol, vinyl carbinol, n-propyl alcohol, 2-propyl alcohol, 2-butanols, uncle-butanols and the phenol.
The used salt of above-mentioned reaction can be one of in Quilonum Retard, yellow soda ash, salt of wormwood and the cesium carbonate; See with yellow soda ash to be good from the cost aspect.
Described alkoxide or phenates can be potassium, the sodium salts of methyl alcohol, ethanol, propyl alcohol, butanols, phenol.
Described alkoxide or phenates are good with sodium methylate, sodium ethylate, sodium phenylate.
Above-mentioned organic solvent can be chosen any one kind of them in hexane, Skellysolve A, hexanaphthene, THF and toluene; See with hexane to be good from the cost aspect.
Said pentachloro-alkoxyl group or phenoxy ring three phosphonitriles and fluorizating agent carry out fluoridation in organic solvent, generated to contain five Fluoroalkyloxies or phenoxy ring three phosphonitriles; To make and contain five Fluoroalkyloxies or phenoxy ring three phosphonitrile products distill, distillate by product and solvent after, obtain five Fluoroalkyloxies or phenoxy ring three phosphonitriles.
Above-mentioned fluorizating agent is from Sodium Fluoride, Potassium monofluoride, lithium fluoride and cesium fluoride, to select.Seeing from reactive and cost aspect, is good with Sodium Fluoride.
Above-mentioned fluoridation is under 40～100 ℃ of temperature condition, to react 2～7 hours.When fluoridation, add a spot of (PNF2) 3, can effectively promote reaction, can in lower temperature (40～50 ℃) and shorter time, accomplish and react.
The organic solvent of above-mentioned fluoridation can be chosen any one kind of them or two kinds in dinethylformamide and the THF etc. at acetonitrile, Nitromethane 99Min., N.
It is raw material with the hexachlorocyclotriphosphazene that the present invention provides a kind of; A chlorine atom that in organic solvent, replaces on the hexachlorocyclotriphosphazene with nucleophilic reagent alkoxide (or phenates) earlier obtains pentachloro-alkane (or benzene) oxygen basic ring three phosphonitriles, then carries out the preparation method of five fluothane (or benzene) oxygen basic ring, three phosphonitriles of fluoridation with fluorizating agent.Its technology is easy, unharmful substance generates in the preparation process.Phosphazene derivative (PNX of the present invention
2)
3X in, at least one is a kind of in alkoxyl group and the phenoxy, other five is fluorine element.
Embodiment
Embodiment 1
With 348g (1mol) hexachlorocyclotriphosphazene crystal; Hexane places and has whisking appliance, TM, returns the 500ml three-necked bottle that heats up in a steamer prolong; Be stirred to dissolving evenly; 70 ℃ of temperature condition down with 50g (98%) ethanol and 110g yellow soda ash reaction 5 hours, warp is made with extra care and is obtained phosphazene derivative---oxyethyl group pentachloro-ring three phosphonitriles.
In the 350g acetonitrile, constantly stir above-mentioned oxyethyl group pentachloro-ring three phosphonitriles that obtain and add 210gNaF down, under 80 ℃ of temperature condition, carry out 5 hours fluoridation after, distillation obtains oxyethyl group five fluorine rings three phosphonitrile (PNF
2)
3
Embodiment 2
With 348g hexachlorocyclotriphosphazene crystal; Hexane places and has whisking appliance, TM, returns the 500ml three-necked bottle that heats up in a steamer prolong, is stirred to dissolving evenly, and 70 ℃ of temperature condition reacted 5 hours with the 68g sodium ethylate down; Distill refining phosphazene derivative---oxyethyl group pentachloro-ring three phosphonitriles that obtain.
In the 350g acetonitrile, constantly stir above-mentioned oxyethyl group pentachloro-ring three phosphonitriles that obtain and add 210gNaF down, under 80 ℃ of temperature condition, carry out 5 hours fluoridation after, distillation obtains oxyethyl group five fluorine rings three phosphonitrile (PNF
2)
3
Embodiment 3
With 174g (0.5mol) hexachlorocyclotriphosphazene crystal; Hexane places and has whisking appliance, TM, returns the 200ml three-necked bottle that heats up in a steamer prolong; Be stirred to dissolving evenly; 70 ℃ of temperature condition reacted 5 hours with 16g methyl alcohol and 55g yellow soda ash down, distilled, and made with extra care and obtained phosphazene derivative---methoxyl group pentachloro-ring three phosphonitriles.
In the 200g acetonitrile, constantly stir above-mentioned methoxyl group pentachloro-ring three phosphonitriles that obtain and add 105gNaF down, under 80 ℃ of temperature condition, carry out 5 hours fluoridation after, distillation obtains methoxyl group five fluorine rings three phosphonitrile (PNF
2)
3
Embodiment 4
With 174g hexachlorocyclotriphosphazene crystal; Hexane places and has whisking appliance, TM, returns the 200ml three-necked bottle that heats up in a steamer prolong, is stirred to dissolving evenly, and 70 ℃ of temperature condition reacted 5 hours with the 27g sodium methylate down; Distill refining phosphazene derivative---methoxyl group pentachloro-ring three phosphonitriles that obtain.
In the 200g acetonitrile, constantly stir above-mentioned methoxyl group pentachloro-ring three phosphonitriles that obtain and add 105gNaF down, under 80 ℃ of temperature condition, carry out 5 hours fluoridation after, distillation obtains methoxyl group five fluorine rings three phosphonitrile (PNF
2)
3
Embodiment 5
With 100g hexachlorocyclotriphosphazene crystal; 300 mL THFs place and have whisking appliance, TM, return the 500ml three-necked bottle that heats up in a steamer prolong, are stirred to dissolving evenly, under 70 ℃ of temperature condition; In reaction flask, splash into 120 mL tetrahydrofuran solutions of 33.2 g (0.28 mo l) sodium phenylate; Time spent 0.5 h is heated to 50 insulation reaction, 1.5 h with reaction solution after drip finishing, and sodium phenylate reacts completely.Distill refining phosphazene derivative---phenoxy pentachloro-ring three phosphonitriles that obtain.
In the 200g acetonitrile, constantly stir above-mentioned phenoxy pentachloro-ring three phosphonitriles that obtain and add 60gNaF down, under 80 ℃ of temperature condition, carry out 5 hours fluoridation after, distillation obtains phenoxy five fluorine rings three phosphonitrile (PNF
2)
3
Claims (10)
1. the preparation method of Fluoroalkyloxy or phenoxy ring three phosphonitriles is characterized in that: comprise following steps:
A. in organic solvent, make with a chlorine atom on nucleophilic reagent alkoxide or the phenates replacement hexachlorocyclotriphosphazene earlier and contain pentachloro-alkoxyl group or phenoxy ring three phosphonitrile products; Then it is distilled; After distillating by product and solvent, obtain pentachloro-alkoxyl group or phenoxy ring three phosphonitriles;
B. then will go up the pentachloro-alkoxyl group that obtains of step or phenoxy ring three phosphonitriles and fluorizating agent carries out fluoridation and makes and contain five Fluoroalkyloxies or phenoxy ring three phosphonitrile products; After then it being distillated by product and solvent, obtain five Fluoroalkyloxies or phenoxy ring three phosphonitriles.
2. according to the preparation method of described five Fluoroalkyloxies of claim 1 or phenoxy ring three phosphonitriles, it is characterized in that: it is potassium, the sodium salt of methyl alcohol, ethanol, propyl alcohol, butanols, phenol that described alkoxide or phenates adopt.
3. according to the preparation method of described five Fluoroalkyloxies of claim 2 or phenoxy ring three phosphonitriles, it is characterized in that: described alkoxide or phenates are good with sodium methylate, sodium ethylate, sodium phenylate.
4. the preparation method of five Fluoroalkyloxies according to claim 1 or phenoxy ring three phosphonitriles is characterized in that: the temperature of the reaction of said step a is 30～90 ℃, and is better at 50～80 ℃.
5. the preparation method of five Fluoroalkyloxies according to claim 1 or phenoxy ring three phosphonitriles is characterized in that: the reaction times of said step a is 3～10 hours, and 5～8 hours better.
6. the preparation method of five Fluoroalkyloxies according to claim 1 or phenoxy ring three phosphonitriles is characterized in that: the organic solvent that said step a adopts is to choose any one kind of them in hexane, Skellysolve A, hexanaphthene, THF and the toluene.
7. the preparation method of five Fluoroalkyloxies according to claim 1 or phenoxy ring three phosphonitriles is characterized in that: said fluorizating agent adopts in Sodium Fluoride, Potassium monofluoride, lithium fluoride and the cesium fluoride any.
8. the preparation method of five Fluoroalkyloxies according to claim 1 or phenoxy ring three phosphonitriles is characterized in that: the fluoridation of said step b is under 40～100 ℃ of temperature condition, to react 2～7 hours.
9. the preparation method of five Fluoroalkyloxies according to claim 1 or phenoxy ring three phosphonitriles is characterized in that: said step b adds a spot of (PNF when fluoridation
2)
3, can effectively promote reaction, can in lower temperature and shorter time, accomplish reaction.
10. the preparation method of five Fluoroalkyloxies according to claim 1 or phenoxy ring three phosphonitriles; It is characterized in that: the organic solvent in the fluoridation of said step b adopts acetonitrile, Nitromethane 99Min., N, chooses any one kind of them or two kinds in dinethylformamide and the THF etc.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103214523A (en) * | 2013-04-01 | 2013-07-24 | 广州鸿森材料有限公司 | Preparation and use methods of high-temperature lithium-ion electrolyte additive and lithium ion battery containing additive |
| CN105732718A (en) * | 2016-03-22 | 2016-07-06 | 山东大学 | Synthesis method of fluorocyclotriphosphazene |
| CN106518928A (en) * | 2016-10-27 | 2017-03-22 | 湖南师范大学 | A synthetic method of alkoxy(pentafluoro) or phenoxyl(pentafluoro) cyclotriphosphazene |
| CN107056841A (en) * | 2017-06-19 | 2017-08-18 | 山东永浩新材料科技有限公司 | A kind of preparation method of the phosphonitrile of five fluorine ring of alkoxy three |
| CN107108673A (en) * | 2015-04-14 | 2017-08-29 | 山东泽世新材料科技有限公司 | A kind of fluorination process of hexachlorocyclotriph,sphazene and its derivative |
| CN108314694A (en) * | 2018-02-02 | 2018-07-24 | 苏州贺康新材料科技有限公司 | A kind of preparation method of lithium battery electrolytes fire retardant |
| CN110845540A (en) * | 2019-11-07 | 2020-02-28 | 山东省海洋化工科学研究院 | Preparation method and preparation device of hexaphenoxycyclotriphosphazene |
| CN115873039A (en) * | 2021-09-29 | 2023-03-31 | 浙江蓝天环保高科技股份有限公司 | Method for preparing alkoxy (pentafluoro) cyclotriphosphazene by one-pot method |
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Cited By (12)
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| CN103214523A (en) * | 2013-04-01 | 2013-07-24 | 广州鸿森材料有限公司 | Preparation and use methods of high-temperature lithium-ion electrolyte additive and lithium ion battery containing additive |
| CN103214523B (en) * | 2013-04-01 | 2016-01-06 | 广州鸿森材料有限公司 | A kind of method of preparation and use and the lithium ion battery comprising this additive of high temp. lithium ion electrolysis additive |
| CN107108673A (en) * | 2015-04-14 | 2017-08-29 | 山东泽世新材料科技有限公司 | A kind of fluorination process of hexachlorocyclotriph,sphazene and its derivative |
| JP2018510130A (en) * | 2015-04-14 | 2018-04-12 | ▲ず▼博▲藍▼印化工有限公司 | Fluorination treatment method of phosphorus nitride chloride trimer and derivatives |
| US10017530B2 (en) | 2015-04-14 | 2018-07-10 | Shandong Zeshi New Materials Technology Co., Ltd. | Fluorination method for phosphonitrilic chloride trimer and its derivatives |
| CN105732718A (en) * | 2016-03-22 | 2016-07-06 | 山东大学 | Synthesis method of fluorocyclotriphosphazene |
| CN105732718B (en) * | 2016-03-22 | 2017-12-01 | 山东大学 | A kind of synthetic method of the phosphonitrile of fluoro ring three |
| CN106518928A (en) * | 2016-10-27 | 2017-03-22 | 湖南师范大学 | A synthetic method of alkoxy(pentafluoro) or phenoxyl(pentafluoro) cyclotriphosphazene |
| CN107056841A (en) * | 2017-06-19 | 2017-08-18 | 山东永浩新材料科技有限公司 | A kind of preparation method of the phosphonitrile of five fluorine ring of alkoxy three |
| CN108314694A (en) * | 2018-02-02 | 2018-07-24 | 苏州贺康新材料科技有限公司 | A kind of preparation method of lithium battery electrolytes fire retardant |
| CN110845540A (en) * | 2019-11-07 | 2020-02-28 | 山东省海洋化工科学研究院 | Preparation method and preparation device of hexaphenoxycyclotriphosphazene |
| CN115873039A (en) * | 2021-09-29 | 2023-03-31 | 浙江蓝天环保高科技股份有限公司 | Method for preparing alkoxy (pentafluoro) cyclotriphosphazene by one-pot method |
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Effective date of registration: 20220905 Address after: 354000 Jintang Industrial Park, Shaowu City, Nanping City, Fujian Province Patentee after: Fujian Shaowu Chuangxin New Material Co.,Ltd. Address before: No.155, Yangqiao West Road, Gulou District, Fuzhou City, Fujian Province Patentee before: FUJIAN CHUANGXIN SCIENCE AND DEVELOPS CO.,LTD. |