JP5652184B2 - Method for producing fluorophosphazene derivative - Google Patents

Description

  The present invention relates to a method for producing a fluorophosphazene derivative.

  Among compounds having an NP bond, a compound called phosphazene is used as a flame retardant, a heat-resistant material, a catalyst, a separating agent, a stabilizer, and the like. In particular, it is widely used for flame retardants and heat-resistant materials. In recent years, fluorophosphazene derivatives have been added to non-aqueous electrolytes to give flame retardants to non-aqueous electrolytes. It is also used in a non-aqueous electrolyte secondary battery that greatly reduces the risk of the occurrence (see Patent Document 1). According to this patent document, by introducing an alkoxy group or the like into perfluorocyclopolyphosphazene, a fluorophosphazene derivative is produced and added to a non-aqueous electrolyte solution to become an effective flame retardant. The method for producing a fluorophosphazene disclosed in Patent Document 1 involves reacting perfluorocyclopolyphosphazene with an alkali metal alkoxide or reacting a compound having a hydroxyl group in the presence of an alkali metal salt compound.

WO03 / 005479 pamphlet

  However, in the method for producing a fluorophosphazene derivative disclosed in Patent Document 1, when an alkali metal alkoxide is used as a reactant, it is difficult to control the reaction, and an alkoxy group is introduced at a plurality of locations, and fluorophosphazene other than the target product is obtained. Many derivatives are produced and the yield is lowered. Even when a compound having a hydroxyl group is used as a reactant in the presence of an alkali metal salt compound, the boiling point of the resulting fluorophosphazene derivative approaches the reaction solvent. In some cases, the yield may be reduced. In addition, when the compound having a hydroxyl group, which is a raw material for the alkoxy group to be introduced, is liquid at room temperature, it may be usable as a solvent itself, but there is a concern that it may be difficult to control the reaction. Accordingly, an object of the present invention is to provide an inexpensive and efficient method for producing fluorophosphazene.

  As a result of intensive studies in view of such problems, the present inventors have found a method for efficiently producing a fluorophosphazene derivative from perfluorocyclopolyphosphazene at low cost and have reached the present invention.

That is, the present invention comprises methyl monoglyme, ethyl monoglyme, propyl monoglyme, butyl monoglyme, methyl diglyme, ethyl diglyme, propyl diglyme, butyl diglyme, methyl triglyme, ethyl triglyme, methyltetraglyme. In the presence of at least one glyme selected from the group and a salt compound, a compound having at least one hydroxyl group in the molecular structure is reacted with perfluorocyclopolyphosphazene represented by the following general formula [1]. A fluorophosphazene derivative represented by the following general formula [2] is obtained , and the addition amount of the glymes is 0.0005 to 0.1 of a compound having at least one hydroxyl group in the molecular structure. fluorophosphazene, which is a fold molar A method for producing a conductor.
(PNF ₂ ) _n [1]
(In the formula, n represents 3 to 14.)
(PNR ₂ ) _n [2]
(In the formula, each R is independently a fluorine atom or an alkoxy group, and at least one of all R is an alkoxy group, and n is 3 to 14.)

  In addition, in the method for producing a fluorophosphazene derivative, the alkoxy group is at least one selected from primary, secondary, and tertiary alkoxy groups.

  The salt compound is a method for producing a fluorophosphazene derivative, wherein the salt compound is at least one selected from the group consisting of alkali metal carbonates, bicarbonates, sulfates, and nitrates.

  Moreover, the said reaction is a manufacturing method of the fluoro phosphazene derivative performed by the temperature conditions of 20-80 degreeC for 1 to 72 hours.

  Further, it is a method for producing a fluorophosphazene derivative, wherein the compound having at least one hydroxyl group in the molecular structure is at least one kind selected from primary, secondary or tertiary alcohols.

  The present invention can provide a method for rapidly and efficiently producing a fluorophosphazene derivative used as a flame retardant.

  Hereinafter, the present invention will be described in detail.

The method for producing the fluorophosphazene derivative of the present invention includes methyl monoglyme, ethyl monoglyme, propyl monoglyme, butyl monoglyme, methyl diglyme, ethyl diglyme, propyl diglyme, butyl diglyme, methyl triglyme, and ethyl triglyme. A compound having at least one hydroxyl group in the molecular structure in the presence of at least one glyme selected from the group consisting of methyltetraglyme and a salt compound, and a perfluorocyclopolypolyester represented by the following general formula [1] By reacting with phosphazene, a fluorophosphazene derivative represented by the following general formula [2] is obtained.
(PNF ₂ ) _n [1]
(In the formula, n represents 3 to 14.)
(PNR ₂ ) _n [2]
(In the formula, each R is independently a fluorine atom or an alkoxy group, and at least one of all R is an alkoxy group, and n is 3 to 14.)

  Examples of the perfluorocyclopolyphosphazene represented by the general formula [1] include hexafluorocyclotriphosphazene and octafluorocyclotetraphosphazene.

  The organic group represented by R of the fluorophosphazene derivative represented by the general formula [2] is preferably an alkoxy group. It is preferable that the organic group is an alkoxy group because the temperature range in which the fluorophosphazene derivative represented by the general formula [2] exists as a liquid becomes wide.

  The alkoxy group is preferably at least one selected from primary, secondary, and tertiary alkoxy groups. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a trifluoroethoxy group, and a hexafluoropropoxy group. Of these, a trifluoroethoxy group and a hexafluoropropoxy group are particularly preferable.

  The reaction is carried out in the presence of a salt compound, methyl monoglyme, ethyl monoglyme, propyl monoglyme, butyl monoglyme, methyl diglyme, ethyl diglyme, propyl diglyme, butyl diglyme, methyl triglyme, ethyl triglyme, methyl It is preferably performed by adding a catalytic amount of at least one glyme selected from the group consisting of tetraglyme. The presence of the salt compound is preferable because the etherification reaction proceeds, and the addition of glymes is preferable because the reaction rate increases.

  The salt compound is preferably at least one selected from the group consisting of alkali metal carbonates, bicarbonates, sulfates, and nitrates. For example, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, lithium sulfate, sodium sulfate, potassium sulfate, cesium sulfate, lithium nitrate, sodium nitrate, potassium nitrate, Examples thereof include cesium nitrate. Among these, lithium carbonate, sodium carbonate, potassium carbonate, and cesium carbonate are particularly preferable. Moreover, said salt compound may be used individually by 1 type, and may be mixed and used for arbitrary ratios combining 2 or more types.

  The amount of the salt compound used is not particularly limited, but hydrogen fluoride generated by the reaction in the present invention can be removed as a fluoride salt. Therefore, among the fluorine atoms of one perfluorocyclopolyphosphazene molecule, When the number of fluorine atoms on the phosphorus atom to be removed is m and the number of alkali metal atoms in one molecule of the alkali metal salt compound is n, the amount of the salt compound used is m / n times that of perfluorocyclopolyphosphazene. The range is from mol to 5 m / n times mol, preferably from 1.5 m / n times mol to 3 m / n times mol. When the amount is less than m / n mole, the reaction does not proceed to the end, which is not preferable. On the other hand, when it is more than 5 m / n mole, there is a problem that it is not economical and solid waste increases.

  The glymes include methyl monoglyme (ethylene glycol dimethyl ether), ethyl monoglyme (ethylene glycol diethyl ether), propyl monoglyme (ethylene glycol dipropyl ether), butyl monoglyme (ethylene glycol dibutyl ether), methyl diglyme (diethylene glycol) Dimethyl ether), ethyl diglyme (diethylene glycol diethyl ether), propyl diglyme (diethylene glycol dipropyl ether), butyl diglyme (diethylene glycol dibutyl ether), methyl triglyme (triethylene glycol dimethyl ether), ethyl triglyme (triethylene glycol diethyl ether) ), Methyltetraglyme (tetraethylene glycol dimethyl) It is preferably at least one compound selected from the group consisting of ether).

  Among the above-mentioned chain glycol ethers, when ethylene glycol dimethyl ether (methyl monoglyme), triethylene glycol dimethyl ether (methyl triglyme) or tetraethylene glycol dimethyl ether (methyl tetraglyme) is used, the fluorophosphazene derivative can be obtained in a short time and with high yield. It is particularly preferable because it can be obtained at a rate.

  In addition to the glymes, a catalytic amount of cyclic carbonate, chain carbonate, cyclic ester, chain ester, or cyclic ether may be additionally added. Specific examples of the above include cyclic carbonates such as propylene carbonate, ethylene carbonate and butylene carbonate, chain carbonates such as diethyl carbonate, dimethyl carbonate and ethyl methyl carbonate, cyclic esters such as γ-butyrolactone and γ-valerolactone, methyl acetate, Examples thereof include chain esters such as ethyl acetate and methyl propionate, and cyclic ethers such as 12-crown-4, 15-crown-5, and 18-crown-6.

  The amount of the glymes used may be a catalyst amount of 0.0005 to 0.1 times mol, preferably 0.01 to 0.05 times mol of the compound having a hydroxyl group. When the amount is less than 0.0005 moles, the progress of the reaction becomes very slow and is not efficient, which is not preferable. When the amount is more than 0.1 times mol, an alkoxy group is introduced more than expected and the yield is lowered, which is not preferable.

  The reaction is preferably performed at a temperature of 20 to 80 ° C. for 1 to 72 hours. When the temperature is lower than 20 ° C., it is not preferable because perfluorocyclopolyphosphazene tends to be solid and the reaction tends to be difficult, and when it exceeds 80 ° C., the reaction tends to be difficult to control. 20-80 degreeC is preferable from the point of manufacturing efficiency, and 25-50 degreeC is more preferable. The reaction time is preferably 1 to 72 hours, more preferably 1 to 60 hours from the viewpoint of productivity. Further, the yield of the fluorophosphazene derivative of the present invention is preferably 50% or more, particularly preferably 60% or more, from the viewpoint of productivity.

  The reaction is carried out in a closed system, and the pressure is not particularly limited, but normal pressure is preferred. In addition, in order to avoid hydrolysis of the raw material perfluorocyclopolyphosphazene and the generated fluorophosphazene derivative by the action of a salt compound and water, the reaction should be performed in an inert gas atmosphere such as nitrogen. Is preferred.

  The compound having at least one hydroxyl group in the molecular structure is preferably a primary, secondary or tertiary alcohol.

  The compound having at least one hydroxyl group is not particularly limited. For example, methanol, ethanol, propanol (n-propanol, 2-propanol, etc.), allyl alcohol, propargyl alcohol, butanol (n-butanol, 2- Butanol, tert-butanol, etc.), 2,2,2-trifluoroethanol, 2,2,3,3,3-pentafluoropropanol, 1,1,1,3,3,3-hexafluoro-2-propanol 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol, 1,1,1,3,3,3-hexafluoro-2-vinyl-2-propanol, 1,1 , 1,3,3,3-hexafluoro-2-phenyl-2-propanol. Moreover, the said compound which has a hydroxyl group may be used individually by 1 type, and may be mixed and used for arbitrary ratios combining 2 or more types.

  The amount of the compound having at least one hydroxyl group is not particularly limited. However, when it is desired to react with one fluorine atom of perfluorocyclopolyphosphazene, it is 1/6 to 1/2 times that of perfluorocyclopolyphosphazene. Mole is preferable, and when it is equimolar or more, the amount of disubstituted or higher products is increased, which is not preferable. At this time, excess perfluorocyclopolyphosphazene is recovered by distillation and can be reused.

（式［４］中Ａはそれぞれ独立して、ハロゲン原子、低級アルキル基、低級アルコキシ基、ハロゲンで置換された低級アルキル基、及び、ハロゲンで置換された低級アルコキシ基からなる群から選ばれる少なくとも１つの基を示し、ｍは０または１〜５の正の整数である） In addition to the primary, secondary, or tertiary alcohols, phenols represented by the following general formula [4] may be additionally added.

(In Formula [4], each A is independently selected from the group consisting of a halogen atom, a lower alkyl group, a lower alkoxy group, a lower alkyl group substituted with a halogen, and a lower alkoxy group substituted with a halogen. Represents one group, and m is 0 or a positive integer of 1 to 5)

  Although there is no restriction | limiting in particular as said phenols, For example, phenol, acetylphenol (4-acetylphenol etc.), methoxyphenol (4-methoxyphenol etc.), nitrophenol (4-nitrophenol etc.), hydroxybenzoic acid ( Salicylic acid etc.), fluorophenol (4-fluorophenol etc.), chlorophenol (4-chlorophenol etc.), bromophenol (4-bromophenol etc.), iodophenol (4-iodophenol etc.), cresol (p-cresol etc.) ), Ethylphenol (such as 4-ethylphenol), propylphenol (such as 4-propylphenol), and trifluoromethylphenol (such as 4-trifluoromethylphenol).

  In the method for producing a fluorophosphazene derivative of the present invention, for example, a solvent, a catalyst, and a flame retardant component may be added to the raw material as long as the purpose of the obtained fluorophosphazene derivative is not impaired. However, if a solvent is present, the raw material, reaction product, and solvent become three components, and the efficiency of separation tends to decrease. Therefore, the smaller the solvent component, the better, and the production of a fluorophosphazene derivative without solvent is performed. Is more preferable.

  Moreover, a fluorophosphazene derivative can be obtained by distilling and purifying the reaction solution after the reaction. The distillation purification is preferably carried out at normal pressure by attaching a distillation column such as a Vigreux column or packed column to the distillation purification vessel and a fractionation column.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples.

Example 1
[Synthesis of fluorophosphazene derivatives]
A 1 L three-necked glass flask was equipped with a three-way cock, and the flask was (PNF ₂ ) ₃ (750 mmol), 2,2,2-trifluoroethanol (250 mmol), sodium carbonate (salt compound: Na ₂ CO ₃ , 375 mmol), It was added sequentially methyl triglyme (2.5 mmol), under nitrogen atmosphere, atmospheric pressure, allowed to react for 24 hours at 25 ° C., at distillation first fraction a _{(PNF 2) 3} was separated and removed, main fraction having the following structure The fluorophosphazene derivative 1 represented by the formula was obtained with a yield of 81%. The impurities were unreacted raw materials, and the generation of multi-substituents other than the target product was not confirmed by NMR spectrum, confirming excellent reaction controllability. The results are shown in Table 1.

(Example 2)
Example 1 except that 2,1,2-trifluoroethanol was replaced with 1,1,1,3,3,3-hexafluoro-2-propanol in “Synthesis of fluorophosphazene derivative” in Example 1. In the same manner as above, a fluorophosphazene derivative 2 represented by the following structural formula was obtained in a yield of 77%. The impurities were unreacted raw materials, and the production of multi-substitution products other than the target product was not confirmed, confirming excellent reaction controllability. The results are shown in Table 1.

Example 3
Except that 2,1,2-trifluoroethanol was replaced with 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol in “Synthesis of fluorophosphazene derivative” in Example 1. In the same manner as in Example 1, a fluorophosphazene derivative 3 represented by the following structural formula was obtained in a yield of 76%. The impurities were unreacted raw materials, and the production of multi-substitution products other than the target product was not confirmed, confirming excellent reaction controllability. The results are shown in Table 1.

Example 4
Except that 2,1,2-trifluoroethanol was replaced with 1,1,1,3,3,3-hexafluoro-2-vinyl-2-propanol in “Synthesis of fluorophosphazene derivative” in Example 1. In the same manner as in Example 1, a fluorophosphazene derivative 4 represented by the following structural formula was obtained in a yield of 73%. The impurities were unreacted raw materials, and the production of multi-substitution products other than the target product was not confirmed, confirming excellent reaction controllability. The results are shown in Table 1.

(Example 5)
A fluorophosphazene derivative 1 was obtained in a yield of 82% in the same manner as in Example 1 except that methyltriglyme was replaced with methyltetraglyme in “Synthesis of fluorophosphazene derivative” in Example 1. The impurities were unreacted raw materials, and the production of multi-substitution products other than the target product was not confirmed, confirming excellent reaction controllability. The results are shown in Table 1.

(Example 6)
Fluorophosphazene derivative 2 was obtained in 79% yield in the same manner as in Example 2 except that methyltriglyme was replaced with methyltetraglyme in “Synthesis of fluorophosphazene derivative” in Example 2. The impurities were unreacted raw materials, and the production of multi-substitution products other than the target product was not confirmed, confirming excellent reaction controllability. The results are shown in Table 1.

(Example 7)
In “Synthesis of fluorophosphazene derivative” in Example 1, 2,1,2-trifluoroethanol was changed to 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanol and methyltriglyme The fluorophosphazene derivative 5 represented by the following structural formula was obtained in a yield of 80% in the same manner as in Example 1 except that was replaced with methyl monoglyme. The impurities were unreacted raw materials, and the production of multi-substitution products other than the target product was not confirmed, confirming excellent reaction controllability. The results are shown in Table 1.

(Example 8)
In “Synthesis of fluorophosphazene derivative” in Example 2, the reaction time was changed to 24 hours and 12 hours, and sodium carbonate was replaced with potassium carbonate (salt compound: K ₂ CO ₃ ). The fluorophosphazene derivative 2 was obtained with a yield of 68%. The impurities were unreacted raw materials, and the production of multi-substitution products other than the target product was not confirmed, confirming excellent reaction controllability. The results are shown in Table 1.

Example 9
In “Synthesis of fluorophosphazene derivative” in Example 2, the reaction time was changed from 24 hours to 48 hours, and sodium carbonate was replaced with lithium carbonate (salt compound: Li ₂ CO ₃ ). The fluorophosphazene derivative 2 was obtained with a yield of 71%. The impurities were unreacted raw materials, and the production of multi-substitution products other than the target product was not confirmed, confirming excellent reaction controllability. The results are shown in Table 1.

(Example 10)
In “Synthesis of fluorophosphazene derivative” in Example 2, the fluorophosphazene derivative 2 was obtained in the same manner as in Example 2 except that the reaction temperature 25 ° C. was changed to 40 ° C. and the reaction time 24 hours was changed to 2 hours. Obtained at 66%. The impurities were unreacted raw materials, and the production of multi-substitution products other than the target product was not confirmed, confirming excellent reaction controllability. The results are shown in Table 1.

(Example 11)
In Example 2 “Synthesis of fluorophosphazene derivative”, the same procedure as in Example 2 was conducted except that 0.01-fold mol of methyltriglyme was changed to 0.001-fold mol and the reaction time was changed to 48 hours. The fluorophosphazene derivative 2 was obtained with a yield of 75%. The impurities were unreacted raw materials, and the production of multi-substitution products other than the target product was not confirmed, confirming excellent reaction controllability. The results are shown in Table 1.

(Example 12)
In Example 2 "Synthesis of fluorophosphazene derivative", the same procedure as in Example 2 was carried out except that 0.01-fold mol of methyltriglyme was changed to 0.05-fold mol and the reaction time was changed to 6 hours. The fluorophosphazene derivative 2 was obtained with a yield of 70%. The impurities were unreacted raw materials, and the production of multi-substitution products other than the target product was not confirmed, confirming excellent reaction controllability. The results are shown in Table 1.

( Reference Example 13)
In “Synthesis of fluorophosphazene derivative” in Example 2, the same procedure as in Example 2 was conducted, except that 0.01 times mole of methyltriglyme was changed to 0.0001 times mole and the reaction time was changed to 72 hours. The fluorophosphazene derivative 2 was obtained with a yield of 52%. The impurities were unreacted raw materials, and the production of multi-substitution products other than the target product was not confirmed. Thus, it was confirmed that excellent reaction controllability was exhibited, but the reaction took a long time.

( Reference Example 14)
Fluorophosphazene was prepared in the same manner as in Example 2 except that in the “synthesis of fluorophosphazene derivative” in Example 2, 0.01 times mole of methyltriglyme was changed to 1 time mole and the reaction time was changed to 1 hour. Derivative 2 was obtained with a yield of 50%. The impurities were unreacted raw materials and polysubstituted products other than the target product.

(Comparative Example 1)
In Example 2 “Synthesis of fluorophosphazene derivative”, the reaction temperature was changed from 25 ° C. to 80 ° C., the reaction time was changed from 24 hours to 5 hours, methyltriglyme was not added, and hexane was used as a solvent. In the same manner as in Example 2, fluorophosphazene derivative 2 was obtained with a yield of 40%. In addition, since the impurities were unreacted raw materials and multi-substituted products other than the target product, the reaction controllability was poor. The results are shown in Table 1.

(Comparative Example 2)
In “Synthesis of fluorophosphazene derivative” in Example 2, the reaction temperature was changed from 25 ° C. to 40 ° C., the reaction time was changed from 24 hours to 14 days, and methyltriglyme was not added. Thus, the fluorophosphazene derivative 2 was obtained with a yield of 76%. The impurities were unreacted raw materials, and the production of multi-substitution products other than the target product was not confirmed, so it was confirmed that excellent reaction controllability was exhibited, but the reaction took a long time and was produced. The nature was bad. The results are shown in Table 1.

Claims (5)

At least selected from the group consisting of methyl monoglyme, ethyl monoglyme, propyl monoglyme, butyl monoglyme, methyl diglyme, ethyl diglyme, propyl diglyme, butyl diglyme, methyl triglyme, ethyl triglyme, methyltetraglyme In the presence of one glyme and a salt compound, a compound having at least one hydroxyl group in the molecular structure is reacted with perfluorocyclopolyphosphazene represented by the following general formula [1] to give the following general formula [2 A fluorophosphazene derivative represented by the formula:
The method for producing a fluorophosphazene derivative, wherein the addition amount of the glymes is 0.0005 to 0.1 times mol of the compound having at least one hydroxyl group in the molecular structure.
(PNF ₂ ) _n [1]
(In the formula, n represents 3 to 14.)
(PNR ₂ ) _n [2]
(In the formula, each R is independently a fluorine atom or an alkoxy group, and at least one of all R is an alkoxy group, and n is 3 to 14.) The method for producing a fluorophosphazene derivative according to claim 1, wherein the alkoxy group is at least one selected from primary, secondary, and tertiary alkoxy groups. The fluorophosphazene derivative according to claim 1 or 2, wherein the salt compound is at least one selected from the group consisting of alkali metal carbonates, bicarbonates, sulfates, and nitrates. Manufacturing method. The method for producing a fluorophosphazene derivative according to any one of claims 1 to 3, wherein the reaction is performed at a temperature of 20 to 80 ° C for 1 to 72 hours. 5. The compound having at least one hydroxyl group in the molecular structure is at least one selected from primary, secondary, or tertiary alcohols. A process for producing the described fluorophosphazene derivative.