Method for surface modification of fluororesin

Patent metadata

Field	Value
Publication number	US-12384897-B2
Application number	US-202217580824-A
Country	US
Kind code	B2
Filing date	Jan 21, 2022
Priority date	Sep 27, 2019
Publication date	Aug 12, 2025
Grant date	Aug 12, 2025

Abstract

To provide a method for surface modification of a fluororesin, that enables graft polymerization at a lower temperature than a conventional method.
A method for surface modification of a fluororesin, which comprises reacting a fluororesin with a radical reactive compound in the presence of an organometallic compound.

First claim

What is claimed is:

1. A method for surface modification of a fluororesin, comprising:
reacting a fluororesin with a radical reactive compound in the presence of an organometallic compound,
wherein the fluororesin includes at least one selected from the group consisting of an ethylene-tetrafluoroethylene copolymer and a vinylidene fluoride polymer, and the organometallic compound includes a dialkyl zinc complex.

2. The method according to claim 1 , wherein the fluororesin is in a film form or a particle form.

3. The method according to claim 1 , wherein the fluororesin further includes at least one selected from the group consisting of a perfluoro (alkyl vinyl ether)-tetrafluoroethylene copolymer, a vinyl fluoride polymer, a vinylidene fluoride-hexafluoropropylene copolymer, a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, a tetrafluoroethylene-propylene copolymer, a tetrafluoroethylene-vinylidene fluoride-propylene copolymer, a hexafluoropropylene-tetrafluoroethylene copolymer, an ethylene-hexafluoropropylene-tetrafluoroethylene copolymer, a chlorotrifluoroethylene polymer, an ethylene-chlorotrifluoroethylene copolymer, a polytetrafluoroethylene and a propylene-chlorotrifluoroethylene copolymer.

4. The method according to claim 1 , wherein the organometallic compound includes at least one selected from the group consisting of a diethyl zinc 1,10-phenanthroline complex and a diethyl zinc 2,2′-bipyridine complex.

5. The method according to claim 1 , wherein the radical reactive compound includes at least one selected from the group consisting of (meth)acrylic acid, a (meth)acrylate, a (meth)acrylonitrile, an N-substituted (meth)acrylamide, a vinyl ester, a vinyl ether, an aromatic vinyl compound and a heterocyclic vinyl compound.

6. The method according to claim 1 , wherein the fluororesin and the radical reactive compound are reacted at a reaction temperature of in a range of 5 to 65° C.

7. The method according to claim 1 , wherein the fluororesin is reacted with the radical reactive compound in the presence of the organometallic compound and a co-catalyst.

8. The method according to claim 7 , wherein the co-catalyst is molecular oxygen.

9. The method according to claim 1 , wherein the fluororesin is in a particle form and has an average particle size in a range of 0.1 to 1000 μm.

10. The method according to claim 1 , wherein the method results in a grafting ratio of 0.0005% to 25%, where the grafting ratio={(mass of the fluororesin after the surface modification−mass of the fluororesin before the surface modification)/mass of the fluororesin before the surface modification}×100.

11. The method according to claim 1 , wherein the fluororesin has a water contact angle of less than 95° after the reacting.

12. A method for surface modification of a fluororesin, comprising: reacting a fluororesin with a radical reactive compound in the presence of an organometallic compound, wherein the fluororesin is in a film form or a particle form and includes at least one selected from the group consisting of an ethylene-tetrafluoroethylene copolymer and a vinylidene fluoride polymer, and the organometallic compound includes at least one selected from the group consisting of a diethyl zinc 1,10-phenanthroline complex and a diethyl zinc 2,2′-bipyridine complex.

13. The method according to claim 12 , wherein the fluororesin further includes at least one selected from the group consisting of a perfluoro (alkyl vinyl ether)-tetrafluoroethylene copolymer, a vinyl fluoride polymer, a vinylidene fluoride-hexafluoropropylene copolymer, a tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer, a tetrafluoroethylene-propylene copolymer, a tetrafluoroethylene-vinylidene fluoride-propylene copolymer, a hexafluoropropylene-tetrafluoroethylene copolymer, an ethylene-hexafluoropropylene-tetrafluoroethylene copolymer, a chlorotrifluoroethylene polymer, an ethylene-chlorotrifluoroethylene copolymer, a polytetrafluoroethylene and a propylene-chlorotrifluoroethylene copolymer.

14. The method according to claim 12 , wherein the radical reactive compound includes at least one selected from the group consisting of (meth)acrylic acid, a (meth)acrylate, a (meth)acrylonitrile, an N-substituted (meth)acrylamide, a vinyl ester, a vinyl ether, an aromatic vinyl compound and a heterocyclic vinyl compound.

15. The method according to claim 12 , wherein the fluororesin and the radical reactive compound are reacted at a reaction temperature of in a range of 5 to 65° C.

16. The method according to claim 12 , wherein the fluororesin is reacted with the radical reactive compound in the presence of the organometallic compound and a co-catalyst.

17. The method according to claim 16 , wherein the co-catalyst is molecular oxygen.

18. The method according to claim 12 , wherein the fluororesin is in a particle form and has an average particle size in a range of 0.1 to 1000 μm.

19. The method according to claim 12 , wherein the method results in a grafting ratio

mass
⁢

of
⁢

the
⁢

fluororesin
⁢

after
⁢

the
⁢

surface
⁢

modification

-

mass
⁢

of
⁢

the
⁢

fluororesin
⁢

before
⁢

the
⁢

surface
⁢

modification

mass
⁢

of
⁢

the
⁢

fluororesin
⁢

before
⁢

the
⁢

surface
⁢

modification

×
100

of 0.0005% to 25%.

20. The method accordin

Assignees

• Agc Inc

Inventors

• Sugimoto Ryuichi
• Hoshino Taiki
• Murotani Eisuke
• Otozawa Nobuyuki

Classifications

• C08F2/36

  Polymerisation in solid state · CPC title

• C08L2203/16

  used for films · CPC title

• C08K5/55

  Boron-containing compounds {(C08K5/0091 takes precedence)} · CPC title

• C08K5/3437

  condensed with carbocyclic rings · CPC title

• C08F291/04

  on to halogen-containing macromolecules · CPC title