Method for producing melt-moldable tetrafluoroethylene copolymer
View Patent ↗The claimed invention relates to a method for producing a melt-moldable tetrafluoroethylene copolymer containing repeating units (a) based on tetrafluoroethylene and repeating units (b) based on another fluoromonomer, wherein the amount of the repeating units (a), based on the total mass of the repeating units (a) and the repeating units (b), is from 97.3 to 99.5 mass %, and the volume flow rate of the copolymer is from 0.1 to 1000 mm 3 /s; the process including radical suspension-polymerization of tetrafluoroethylene and the fluoromonomer in an aqueous medium in the presence of a radical polymerization initiator and at least one chain transfer agent selected from the group consisting of methane, ethane, a hydrochlorocarbon, a hydrofluorocarbon and a hydrochlorofluorocarbon.
1. A method for producing a melt-moldable tetrafluoroethylene copolymer comprising:
radical suspension-polymerizing tetrafluoroethylene and perfluoro(alkyl vinyl ether) in an aqueous medium in the presence of
a radical polymerization initiator,
at least one chain transfer agent selected from the group consisting of methane, ethane, a hydrochlorocarbon, a hydrofluorocarbon and a hydrochlorofluorocarbon, and
3 to 32.1 ppm of a fluoroemulsifier, based on the total mass of the aqueous medium,
by charging the perfluoro(alkyl vinyl ether) all at once at the initiation of the polymerization, wherein
said melt-moldable tetrafluoroethylene copolymer comprises repeating units (a) based on tetrafluoroethylene and repeating units (b) based on perfluoro(alkyl vinyl ether), wherein the amount of the repeating units (a) is from 97.4 to 99.5 mass % based on the total mass of the repeating units (a) and the repeating units (b), and the amount of the repeating units (b) is from 0.5 to 2.6 mass % based on the total mass of the repeating units (a) and the repeating units (b),
the melting point of said melt-moldable tetrafluoroethylene copolymer is from 320 to 335° C., and
the volume flow rate of said melt-moldable tetrafluoroethylene copolymer is from 0.1 to 1000 mm 3 /s.
2. The method for producing a melt-moldable tetrafluoroethylene copolymer according to claim 1 , wherein said perfluoro(alkyl vinyl ether) is a perfluoro(propyl vinyl ether).
3. The method for producing a melt-moldable tetrafluoroethylene copolymer according to claim 1 , wherein the chain transfer agent is a compound represented by the following formula (1):
C n H m Cl p F 2n+2−m−p (1),
where n is an integer of 1 to 3, m is an integer of 1 to 6, p is 0 or an integer of 1 to 7, m≦2n+2, and p≦2n+2−m.
4. The method for producing a melt-moldable tetrafluoroethylene copolymer according to claim 1 , wherein the chain transfer agent is dichloromethane, chlorodifluoromethane or ethane.
5. The method for producing a melt-moldable tetrafluoroethylene copolymer according to claim 1 , wherein the amount of the chain transfer agent to be charged is from 0.0001 to 1 in the molar ratio, based on the total monomers charged at the initiation of the polymerization.
6. The method for producing a melt-moldable tetrafluoroethylene copolymer according to claim 1 , wherein the radical polymerization initiator is a water-soluble radical polymerization initiator.
7. The method for producing a melt-moldable tetrafluoroethylene copolymer according to claim 6 , wherein the water-soluble radical polymerization initiator is ammonium persulfate.
8. The method for producing a melt-moldable tetrafluoroethylene copolymer according to claim 1 , wherein the fluoroemulsifier is ammonium perfluorooctanoate, ammonium perfluorohexanoate or F(CF 2 ) 2 OCF 2 CF 2 OCF 2 COONH 4 .
9. The method for producing a melt-moldable tetrafluoroethylene copolymer according to claim 1 , wherein the amount of said perfluoro(alkyl vinyl ether) to be used and present in the polymerization system at the initiation of the polymerization is from 1 to 6 mass % based on the tetrafluoroethylene copolymer to be formed.
10. The method for producing a melt-moldable tetrafluoroethylene copolymer according to claim 1 , wherein the melting point of said melt-moldable tetrafluoroethylene copolymer is from 320 to 330° C.
11. The method for producing a melt-moldable tetrafluoroethylene copolymer according to claim 1 , wherein the melting point of said melt-moldable tetrafluoroethylene copolymer is from 325 to 330° C.
12. The method for producing a melt-moldable tetrafluoroethylene copolymer according to claim 1 , wherein the amount of the fluoroemulsifier, based on the total mass of the aqueous medium, is from 3 to 30 ppm.
13. The method for producing a melt-moldable tetrafluoroethylene copolymer according to claim 1 , wherein the amount of the fluoroemulsifier, based on the total mass of the aqueous medium, is from 5 to 30 ppm.
14. The method for producing a melt-moldable tetrafluoroethylene copolymer according to claim 1 , wherein the amount of the fluoroemulsifier, based on the total mass of the aqueous medium, is from 10 to 30 ppm.