Graft copolymers of a poly(vinylidene fluoride)-based polymer and at least one type of electrically conductive polymer, and methods for forming the graft copolymers

Patent metadata

Field	Value
Publication number	US-9732194-B2
Application number	US-201214364015-A
Country	US
Kind code	B2
Filing date	Dec 7, 2012
Priority date	Dec 9, 2011
Publication date	Aug 15, 2017
Grant date	Aug 15, 2017

Abstract

Methods for forming a graft copolymer of a poly(vinylidene fluoride)-based polymer and at least one type of electrically conductive polymer, wherein the electrically conductive polymer is grafted on the poly(vinylidene fluoride)-based polymer are provided. The methods comprise a) irradiating a poly(vinylidene fluoride)-based polymer with a stream of electrically charged particles; b) forming a solution comprising the irradiated poly(vinylidene fluoride)-based polymer, an electrically conductive monomer and an acid in a suitable solvent; and c) adding an oxidant to the solution to form the graft copolymer. Graft copolymers of a poly(vinylidene fluoride)-based polymer and at least one type of electrically conductive polymer, wherein the electrically conductive polymer is grafted on the poly(vinylidene fluoride)-based polymer, nanocomposite materials comprising the graft copolymer, and multilayer capacitors comprising the nanocomposite material are also provided.

First claim

The invention claimed is:

1. A method for forming a graft copolymer of a poly(vinylidene fluoride)-based polymer and at least one type of electrically conductive polymer, wherein the electrically conductive polymer is grafted on the poly(vinylidene fluoride)-based polymer, the method comprising the following steps a) through c) in sequential order:
a) irradiating a poly(vinylidene fluoride)-based polymer with a stream of electrically charged particles;
b) forming a solution comprising the irradiated poly(vinylidene fluoride)-based polymer, an electrically conductive monomer and an acid in a suitable solvent; and
c) adding an oxidant to the solution to form the graft copolymer.

2. The method according to claim 1 , wherein the electrically charged particles are electrons.

3. The method according to claim 1 , further comprising exposing the irradiated poly(vinylidene fluoride)-based polymer to oxygen prior to step (b) to allow formation of peroxides and/or hydroperoxides on a surface of the polymer.

4. The method according to claim 3 , wherein exposing the irradiated poly(vinylidene fluoride)-based polymer to oxygen comprises placing the irradiated poly(vinylidene fluoride)-based polymer under atmospheric conditions for a time period of at least 30 minutes.

5. The method according to claim 1 , wherein the poly(vinylidene fluoride)-based polymer is selected from the group consisting of poly(vinylidene fluoride) (PVDF), poly(vinylidenefluoride-co-trifluoroethylene) (PVDF-TrFE), poly(vinylidene) flouride-hexafluoropropylene (PVDF-HEP), poly(vinylidene fluoride-chlorotrifluoroethylene) (PVDF-CTFE), poly(vinylidene fluoride-trifluoroethylene-chlorofluoroethylene) (PVDF-TrFE-CFE), derivatives thereof, and mixtures thereof.

6. The method according to claim 5 , wherein the poly(vinylidene fluoride)-based polymer comprises poly(vinylidene fluoride).

7. The method according to claim 1 , wherein the electrically conductive monomer is selected from the group consisting of aniline, pyrrole, thiophene, bisthiophene, furan, para-phenylene, phenylene vinylene, para-phenylene sulfide, thienylene-vinylene, acetylene, indole, carbazole, imidazole, pyridine, pyrene, azulene, naphthalene, derivatives thereof, and mixtures thereof.

8. The method according to claim 7 , wherein the electrically conductive monomer comprises aniline.

9. The method according to claim 1 , wherein the acid is selected from the group consisting of hydrochloric acid, sulfuric acid, dodecylbenzenesulfonic acid, naphthalene-2-sulfonic acid, poly(4-syyrenesufonic acid), and mixtures thereof.

10. The method according to claim 1 , wherein the oxidant is selected from the group consisting of ammonium peroxydisulfate (APS), potassium biiodate (KH(IO 3 ) 2 ), iron (III) chloride, and mixtures thereof.

11. The method according to claim 1 , wherein adding the oxidant to the solution comprises dripping the oxidant in a drop wise fashion into the solution.

12. The method according to claim 1 , further comprising blowing air into the solution after step c) to quench the polymerization reaction.

13. A method of forming a multilayer capacitor, the method comprising
a) coating a layer of a first metal on at least a portion of one surface of a nanocomposite material comprising a graft copolymer formed by the method of claim 1 , the graft copolymer being of a poly(vinylidene fluoride)-based polymer and at least one type of electrically conductive polymer, wherein the electrically conductive polymer is grafted on the poly(vinylidene fluoride)-based polymer;
(b) arranging a plurality of the metal-coated nanocomposite material formed in (a) in a stack such that the metal-coated surfaces do not contact each other but face the same direction; and
(c) coating a layer of a second metal on at least a portion of each of two external surfaces of the stack opposing each other and lateral to the external surface of the stack with the layers of first metal coated thereon to form the multilayer capacitor.

14. The method according to claim 13 , wherein the plurality of metal-coated nanocomposite materials comprises three or more metal-coated nanocomposite materials.

15. The method according to claim 13 , wherein the first metal is selected from the group consisting of platinum, silver, gold, aluminium, nickel, copper, and alloys thereof.

Assignees

• Univ Nanyang Tech

Inventors

• Lee Pooi See
• Kumar Vijay
• Lin Meng-Fang

Classifications

• H01B3/445

  from vinylfluorides or other fluoroethylenic compounds · CPC title

• C08F8/30

  Introducing nitrogen atoms or nitrogen-containing groups · CPC title

• C08F214/22

  Vinylidene fluoride · CPC title

• C08L101/005

  Dendritic macromolecules · CPC title

• C08G73/0266

  Polyanilines or derivatives thereof · CPC title