Fluorination method for phosphonitrilic chloride trimer and its derivatives
View Patent ↗The present invention relates to a fluorination method for phosphonitrilic chloride trimer and its derivatives including using phosphonitrilicchloride or partially substituted phosphonitrilic chloride trimer as raw material to fluorinate with fluorinating agent in an ionic liquid to replace the chlorine in chloro-cyclotriphosphazene molecule. The present invention uses non-volatile and pollution free ionic liquids as solvent, and just controls a distillation temperature to get a hexafluorocyclotriphosphazene or derivatives thereof with high-purity. It overcomes the shortcoming of the average solvent system that the solvent forms azeotrope with products. The post-process is simple. The production rate is high, and the ionic liquid can be recycled. The present invention produces products with high purity.
1. A fluorination method for phosphonitrilic chloride trimer and derivatives thereof, comprising the following steps:
dissolving a phosphonitrilic chloride trimer or derivatives thereof into an ionic liquid, adding a fluorinating agent to obtain a solution, and maintaining the solution in a temperature for fluorination; and,
distilling the solution after fluorination at atmospheric pressure to get a hexafluorocyclotriphosphazene or derivatives thereof;
wherein a chemical formula of the phosphonitrilic chloride trimer and derivatives thereof is:
wherein each one of S 1 -S 6 is selected from the group consisting of alkyl, alkoxy, fluoroalkoxy, aryl, carboxyl, hydroxy, cyano, nitro, ether, and halogen; and wherein at least one of S 1 -S 6 is chlorine.
2. The fluorination method for phosphonitrilic chloride trimer and derivatives thereof according to claim 1 , wherein a chemical formula of the ionic liquid is:
wherein each of R1, R2, R3, and R4 is selected from the group consisting of alkyl, alkoxy, aryl, carboxyl, hydroxy, cyano, nitro, ether, hydrogen, and halogen, wherein each of R1, R2, R3, and R4 have 0-20 carbon atoms; wherein at least one of the R1, R2, or R3 is not hydrogen; and
wherein the anion X is one or more selected from the group consisting of F − , PF 6 − , BF 4 − , TFSI − , FSI − , BOB − ClO 4 − .
3. The fluorination method for phosphonitrilic chloride trimer and derivatives thereof according to claim 2 , wherein each of R1, R2 and R3 is selected from the group consisting of methyl, ethyl, propyl, butyl, phenyl, and benzyl.
4. The fluorination method for phosphonitrilic chloride trimer and derivatives thereof according to claim 1 , wherein the fluorinating agent is one or more selected from the group consisting of ammonium fluoride, lithium fluoride, sodium fluoride, potassium fluoride, rubidium fluoride, calcium fluoride, magnesium fluoride, aluminum fluoride, chromium fluoride, iron fluoride, cobalt fluoride, antimony fluoride, nickel fluoride, copper fluoride, zinc fluoride, titanium fluoride and rare earth fluorides.
5. The fluorination method for phosphonitrilic chloride trimer and derivatives thereof according to claim 4 , wherein the fluorinating agent is sodium fluoride and/or potassium fluoride.
6. The fluorination method for phosphonitrilic chloride trimer and derivatives thereof according to claim 1 , wherein the temperature for fluorination is 10-300° C., the fluorination is carried out for 2-98 hours and a temperature for distillation is 40-300° C.
7. The fluorination method for phosphonitrilic chloride trimer and derivatives thereof according to claim 1 , wherein the temperature for fluorination is 0° C.-130° C., the fluorination is carried for a time duration of 12-15 hours and the temperature for distillation is 10° C. higher than the boiling point of the product.