Terminal group conversion method and terminal stabilizing method
View Patent ↗To provide a terminal group conversion method and a terminal stabilizing method, which are capable of converting unstable terminal groups in a fluorinated polymer to carboxylic acid fluoride groups at a high conversion rate. A fluorinated polymer is heated at from 200 to 400° C. for at least one hour in the presence of at least 50 mol of molecular oxygen per 1 mol of unstable terminal groups in the fluorinated polymer, to convert from 50 to 100 mol % of the unstable terminal groups to carboxylic acid fluoride groups.
1. A method to prepare a fluorinated polymer having perfluoromethyl terminal groups, comprising:
heating a fluorinated polymer at from 200 to 400° C. for at least one hour in the presence of molecular oxygen to convert from 50 to 100 mol % of terminal groups comprising units of a polymerization initiator, a chain transfer agent or a dispersion stabilizer to carboxylic acid fluoride groups (—COF); and
reacting molecular fluorine with the fluorinated polymer comprising the carboxylic acid fluoride groups to convert the carboxylic acid fluoride groups to perfluoromethyl groups;
wherein
in the reaction of molecular fluorine with the fluorinated polymer comprising the carboxylic acid fluoride groups the fluorine gas is dissolved and reacted in a solution of the fluorinated polymer having the carboxylic acid fluoride groups, and
a mol ratio of molecular oxygen to terminal groups comprising units of a polymerization initiator, a chain transfer agent or a dispersion stabilizer is at least 50/1.
2. The method according to claim 1 , wherein the molecular oxygen is supplied at a rate of from 5 to 300 mol/hr to the fluorinated polymer.
3. The method according to claim 1 , wherein a content of the fluorinated polymer having carboxylic acid fluoride groups in the solvent is from 1 to 20 mass %.
4. The method according to claim 1 , wherein the fluorinated polymer comprises an aliphatic ring in its main chain.
5. The method according to claim 1 , wherein the fluorinated polymer is a perfluoro-fluorinated polymer.
6. The method according to claim 1 , wherein a temperature of the reaction of molecular fluorine with the fluorinated polymer comprising the carboxylic acid fluoride groups is from 100 to 300° C.
7. The method according to claim 1 , wherein the solvent for the reaction of molecular fluorine with the fluorinated polymer comprising the carboxylic acid fluoride groups is a fluorinated compound having no H atoms bonded to carbon.
8. The method according to claim 7 wherein the solvent is a perfluorotrialkylamine.