CN112175010B

CN112175010B - Synthesis method of hexafluorocyclotriphosphazene

Info

Publication number: CN112175010B
Application number: CN202011114599.3A
Authority: CN
Inventors: 职慧珍; 何珍妮; 杨锦飞
Original assignee: Nanjing Normal University
Current assignee: Nanjing Normal University
Priority date: 2020-10-16
Filing date: 2020-10-16
Publication date: 2023-07-21
Anticipated expiration: 2040-10-16
Also published as: CN112175010A

Abstract

The invention discloses a synthesis method of hexafluorocyclotriphosphazene, which comprises the following steps: dissolving hexachlorocyclotriphosphazene in an organic solvent, adding a fluorinating agent and a catalyst, carrying out a fluorination reaction, and rectifying to obtain the target product, namely the hexafluorocyclotriphosphazene. The synthesis method of hexafluorocyclotriphosphazene has the advantages of mild reaction temperature, simple and easy operation process, high yield, short time consumption, high purity, green and economical property and convenience for industrial production.

Description

Synthesis method of hexafluorocyclotriphosphazene

Technical Field

The invention belongs to the field of hexafluorocyclotriphosphazene, and particularly relates to a method for synthesizing hexafluorocyclotriphosphazene.

Background

Phosphazene compounds are a class of inorganic-organic hybrid compounds that are alternately arranged from P to N. The phosphazene flame retardant has high thermal decomposition temperature and flame retardant effect due to good synergistic effect between phosphorus and nitrogen, is less in fuming and toxic gas, and is an environment-friendly flame retardant material. Hexachlorocyclotriphosphazene is the most representative of phosphazene compounds, wherein chlorine atoms have higher activity and are easily replaced by a plurality of nucleophiles, so that phosphazene derivatives with various functional groups can be synthesized by using hexachlorocyclotriphosphazene. Hexafluorocyclophosphazene is an important intermediate, and some derivatives of the hexafluorocyclophosphazene are high-end flame retardants, and are widely applied to high-efficiency flame retardance of lithium batteries.

Patent CN109503664a discloses a method for synthesizing hexafluorocyclotriphosphazene: in a nonpolar solvent, under the action of a main catalyst of ethylene glycol dimethyl ether homolog and an auxiliary catalyst of alcohols or phenols, hexachlorocyclotriphosphazene and a fluorinating agent undergo a fluorination reaction to prepare the hexafluorocyclotriphosphazene. However, this synthesis method has the disadvantage of using two catalysts, which increases the cost.

Patent CN105732718A discloses a method for synthesizing hexafluorocyclotriphosphazene: in an organic solvent, under the action of polyethylene glycol or polyethylene glycol dimethyl ether, hexachlorocyclotriphosphazene and a fluorinating agent are used for preparing hexafluorocyclotriphosphazene. However, this method has the disadvantage that the reaction takes a long time.

Patent CN104788495a discloses a fluorination method of hexachlorocyclotriphosphazene and derivatives thereof: dissolving hexachlorocyclotriphosphazene in ionic liquid, namely, taking the ionic liquid as a solvent, adding a fluorinating agent, and carrying out fluorination reaction for 10-16 h at the temperature of 130-280 ℃. The method has the following defects: the reaction temperature is higher and the reaction time is long.

Disclosure of Invention

The invention aims to: aiming at the problems existing in the prior art, the invention provides the synthesis method of the hexafluorocyclotriphosphazene, which has the advantages of mild reaction conditions, simple and easy operation, high yield, short time consumption, high purity, green and economical property and convenient industrial production.

The technical scheme is as follows: in order to achieve the above object, the synthesis method of hexafluorocyclotriphosphazene of the present invention comprises the following steps: dissolving hexachlorocyclotriphosphazene in an organic solvent, adding a fluorinating agent and a catalyst, carrying out rectification (ice water bath condensation) after carrying out fluorination reaction, and obtaining the target product of hexafluorocyclotriphosphazene.

Wherein the organic solvent is selected from any one or more of acetonitrile, 1, 4-dioxane, n-hexane, acetone, cyclohexane and tetrahydrofuran.

Preferably, the organic solvent is added in an amount of 50% or less in terms of a solid content ratio (i.e., the mass of the solid hexachlorocyclotriphosphazene and the fluorinating agent is the total mass of the solid and the organic solvent).

Wherein the fluorinating agent is selected from potassium fluoride, sodium fluoride or lithium fluoride.

Wherein, the mol ratio of hexachlorocyclotriphosphazene to fluorinating agent is 1: (6.1-6.5).

Wherein the catalyst is an ionic liquid catalyst and is selected from any one of [ Nbmin ] OH, [ Mmim ] DMP and [ Bmim ] OH.

Wherein: preparation of [ Mmim ] DMP ionic liquid according to related literature Hou Yifeng. Study of alkaline ionic liquid to effectively remove lignin from tobacco stems [ J ]. University of Hunan university, month 12, volume 44, 12 in 2017, wherein the catalyst is mainly used to remove lignin from tobacco stems.

The method comprises the steps of preparing [ Nbmm ] OH ionic liquid, wang Jilin, wang Lulu, liu Xiaojing and the like according to related literature, and synthesizing methyl oleate [ J ]. Fuel chemistry report, 2013, 41 (1): 85-90, wherein the catalyst is mainly applied to catalytic synthesis of methyl oleate.

According to the related literature, [ Bmim ] OH ionic liquid is prepared, xu Qiguang, wang Yanjun, zhang and Huang Chongpin. Basic ionic liquid [ BMIM ] OH catalyzes the reaction kinetics study [ J ] industrial catalysis, volume 22, 12 of 12 months 2014. Wherein the ionic liquid catalyzes the reaction kinetics of the oxidation of m-diisopropylbenzene.

Wherein the dosage of the catalyst is 0.01-0.05% of the mass of hexachlorocyclotriphosphazene.

Wherein the temperature of the fluorination reaction is 20-50 ℃ and the time is 2-3h. Preferably, the temperature of the reaction is 30-35 ℃.

The hexafluoro-cyclotriphosphazene synthesized by the method for synthesizing hexafluoro-cyclotriphosphazene.

The structural formula of hexafluorocyclotriphosphazene is as follows:

the application of the hexafluoro-cyclotriphosphazene synthesized by the synthesis method of the hexafluoro-cyclotriphosphazene in the lithium ion battery is provided.

The invention relates to a synthesis method for preparing hexafluoro-cyclotriphosphazene, which is characterized in that under the action of an organic solvent and a catalyst, a fluorinating agent and hexachloro-cyclotriphosphazene undergo a fluorination reaction, six chlorine atoms on the hexachloro-cyclotriphosphazene are replaced by fluorine, and then the hexafluoro-cyclotriphosphazene is obtained through rectification.

Specifically, the reaction process in the invention is as follows:

the beneficial effects are that: compared with the prior art, the invention has the following advantages:

the invention provides a brand new method for synthesizing hexafluorocyclotriphosphazene, which has the advantages of mild reaction temperature, simple and easy operation process, high yield, short reaction time, simple post-treatment, less byproducts, high purity, green and economic performance and convenient industrialized production in the whole synthesis process. The method for synthesizing the hexafluoro-cyclotriphosphazene can be used for synthesizing the hexafluoro-cyclotriphosphazene with high yield and high efficiency and can be applied to lithium ion batteries.

Drawings

FIG. 1 is a liquid phase diagram of hexachlorocyclotriphosphazene as a raw material in example 1;

FIG. 2 is a liquid phase diagram of the product hexafluorocyclotriphosphazene of example 1;

FIG. 3 is a mass spectrum of the product hexafluorocyclotriphosphazene in example 1.

Detailed Description

The present invention will be described in detail with reference to specific examples.

The experimental methods described in the examples, unless otherwise specified, are all conventional; the reagents and materials, unless otherwise specified, are commercially available. The raw materials used in the present invention are all commercially available.

Example 1

104.3g of hexachlorocyclotriphosphazene, 113.3g of potassium fluoride, 0.011g of ionic liquid catalyst [ Nbmm ] OH and 217.6g of anhydrous acetonitrile are placed in a flask with an electric stirrer, a thermometer and a reflux condenser for reaction at 30 ℃, the reaction is closed after 2 hours, filtration is carried out, and the filtrate is rectified to obtain the hexafluorocyclotriphosphazene with the yield of 98.7 percent.

Wherein the liquid phase diagram of the raw material hexachlorocyclotriphosphazene is shown in figure 1, the liquid phase diagram and the mass spectrum diagram of the product are shown in figures 2 and 3, and the synthesis of the hexafluorocyclotriphosphazene is illustrated.

Example 2

104.3g of hexachlorocyclotriphosphazene, 113.3g of potassium fluoride, 0.011g of ionic liquid catalyst [ Nbmm ] OH and 217.6 anhydrous acetonitrile are placed in a flask with an electric stirrer, a thermometer and a reflux condenser for reaction at 50 ℃, the reaction is closed after 3 hours, the filtration is carried out, and the filtrate is rectified to obtain the hexafluorocyclotriphosphazene with the yield of 98.1 percent.

Example 3

104.3g of hexachlorocyclotriphosphazene, 113.3g of potassium fluoride, 0.011g of ionic liquid catalyst [ Nbmm ] OH and 217.6g of 1, 4-dioxane are placed in a flask with an electric stirrer, a thermometer and a reflux condenser for reaction at 30 ℃ and closed for 2 hours, the reaction is filtered, and the filtrate is rectified to obtain the hexafluorocyclotriphosphazene with the yield of 86 percent.

Example 4

104.3g of hexachlorocyclotriphosphazene, 113.3g of potassium fluoride, 0.014g of ionic liquid catalyst [ Nbmm ] OH and 217.6g of tetrahydrofuran are placed in a flask with an electric stirrer, a thermometer and a reflux condenser for reaction at 50 ℃, the reaction is closed after 3 hours, filtration is carried out, and the filtrate is rectified to obtain the hexafluorocyclotriphosphazene with the yield of 93.3%.

Example 5

104.3g of hexachlorocyclotriphosphazene, 113.3g of potassium fluoride, 0.011g of ionic liquid catalyst [ Nbmm ] OH and 217.6g of cyclohexane are placed in a flask with an electric stirrer, a thermometer and a reflux condenser for reaction at 30 ℃, the reaction is closed after 2 hours, the filtration is carried out, and the filtrate is rectified to obtain the hexafluorocyclotriphosphazene with the yield of 95.8 percent.

Example 6

104.3g of hexachlorocyclotriphosphazene, 113.3g of potassium fluoride, 0.013g of ionic liquid catalyst [ Nbmm ] OH and 217.6g of acetone are placed in a flask with an electric stirrer, a thermometer and a reflux condenser for reaction at 30 ℃, the reaction is closed after 2 hours, the filtration is carried out, and the filtrate is rectified to obtain the hexafluorocyclotriphosphazene with the yield of 96.7 percent.

Example 7

Example 7 was synthesized in the same manner as in example 1, except that: the addition amount of the organic solvent is added according to the solid content of 50%, the fluorinating agent is sodium fluoride, and the mole ratio of hexachlorocyclotriphosphazene to the fluorinating agent is 1:6.1. the ionic liquid catalyst is [ Mmim ] DMP, the catalyst dosage is 0.05% of the mass of hexachlorocyclotriphosphazene, the temperature of the fluorination reaction is 20 ℃, and the time is 3h.

Example 8

Example 8 was synthesized in the same manner as in example 1, except that: the addition amount of the organic solvent is added according to the solid content of 50%, the fluorinating agent is lithium fluoride, and the mole ratio of hexachlorocyclotriphosphazene to the fluorinating agent is 1:6.3. the ionic liquid catalyst is [ Bmim ] OH, the catalyst dosage is 0.03% of the mass of hexachlorocyclotriphosphazene, the temperature of the fluorination reaction is 40 ℃, and the time is 2.5h.

Comparative example 1

104.3g of hexachlorocyclotriphosphazene, 113.3g of potassium fluoride and 217.6g of acetonitrile are placed in a flask with an electric stirrer, a thermometer and a reflux condenser for reaction at 30 ℃ and then the reaction is closed after 2 hours, the filtration is carried out, and the filtrate is rectified to obtain the hexafluorocyclotriphosphazene with the yield of 36.7 percent.

As can be seen from comparative example 1, the present invention synthesizes hexafluorocyclotriphosphazene by fluorination reaction, uses a catalyst with high efficiency, and can obtain a product with higher yield.

Claims

1. The synthesis method of the hexafluorocyclotriphosphazene is characterized by comprising the following steps of: dissolving hexachlorocyclotriphosphazene in an organic solvent, adding a fluorinating agent and a catalyst, and rectifying after fluoridation to obtain a target product, namely hexafluorocyclotriphosphazene;

the catalyst is an ionic liquid catalyst and is selected from any one of [ Nbmin ] OH, [ Mmim ] DMP and [ Bmim ] OH; the catalyst dosage is 0.01% -0.05% of the mass of hexachlorocyclotriphosphazene; the temperature of the fluorination reaction is 20-50 ℃ and the time is 2-3h;

the fluorinating agent is selected from potassium fluoride, sodium fluoride or lithium fluoride.

2. The method for synthesizing hexafluorocyclotriphosphazene according to claim 1, wherein the organic solvent is selected from any one or more of acetonitrile, 1, 4-dioxane, n-hexane, acetone, cyclohexane and tetrahydrofuran.

3. The method for synthesizing hexafluorocyclotriphosphazene according to claim 1, wherein the addition amount of the organic solvent is added according to a solid content of 50% or less; the solid content is the mass of hexachlorocyclotriphosphazene and fluorinating agent accounting for the total mass of solid and organic solvent.

4. The method for synthesizing hexafluorocyclotriphosphazene according to claim 1, wherein the molar ratio of hexachlorocyclotriphosphazene to fluorinating agent is 1: (6.1-6.5).