Conductive polymer films grafted on organic substrates

Patent metadata

Field	Value
Publication number	US-9530965-B2
Application number	US-201414331891-A
Country	US
Kind code	B2
Filing date	Jul 15, 2014
Priority date	Feb 1, 2007
Publication date	Dec 27, 2016
Grant date	Dec 27, 2016

Abstract

One aspect of the invention relates to a linker-free, one-step method of grafting polymer films onto organic substrates, and the films obtained by such a method. In certain embodiments, the grafted polymer films are conductive. In certain embodiments, said grafting method utilizes the ability for Friedel-Crafts catalyst to form radical cations from organic substrates. In one embodiment, the method provides poly-3,4-ethylenedioxythiophene (PEDOT) thin films grafted to organic substrates. In other embodiments, the method is applicable to the polymerization of other monomers to yield conducting polymers, such as polyanilines, polypyrroles, polyfurans, polythiophenes and their derivatives. Remarkably, the polymer films grafted by the inventive methods show enormous increases in adhesion strength. Further, in certain embodiments, polymer patterns were easily obtained using the inventive methods and soft lithography techniques. In certain embodiments, well-defined high-density line-and-space patterns were successfully obtained. In certain embodiments, e.g., when the polymer film is conducting, the obtained conducting polymer pattern grafted on common organic substrates can be used for integrated circuitry in flexible electronics.

First claim

We claim:

1. A method, comprising the steps of:
contacting a pre-surface with a linker which comprises an aryl or heteroaryl moiety, thereby forming a surface comprising aryl or heteroaryl moieties;
contacting said surface with a gaseous metal-containing oxidant, thereby forming an oxidant-enriched surface; and
contacting said oxidant-enriched surface with a gaseous monomer, thereby forming a polymer coating on the surface, wherein the polymer is covalently attached to the surface;
wherein said gaseous monomer is selected from the group consisting of optionally substituted thiophenes, furans, pyrroles, and anilines.

2. The method of claim 1 , wherein said linker is represented by formula V:

wherein, independently for each occurrence,
W is —SiZ 3 or —SR;
X is absent, —O—, —N(R)—, —S—, —C(═O)O—, —C(═O)N(R)—, —C(═O)S—, —S(═O)—, —S(═O) 2 —, —C(R 4 ) 2 —, —C(═O)—, —C(═NR)—, —C(═S)—, —C(R 4 )═C(R 4 )—, —C≡—, -cycloalkyl-, -heterocycloalkyl-, -cycloalkenyl-, -heterocycloalkenyl-, -aryl-, or -heteroaryl-;
Y is -aryl-, or -heteroaryl-;
Z is R 4 , —Cl, —Br, —I, —OR, —NR 2 , —SR, —S(═O)R, or —S(═O) 2 R;
R is -hydrogen, -halogen, -alkyl, -cycloalkyl, -heterocycloalkyl, -alkenyl, -cycloalkenyl, -heterocycloalkenyl, -alkynyl, -cyano, -aryl, or -heteroaryl;
R 4 is -hydrogen, -halogen, -alkyl, -cycloalkyl, -heterocycloalkyl, -alkenyl, -cycloalkenyl, -heterocycloalkenyl, -alkynyl, -aryl, -heteroaryl or —[C(R) 2 ] p —XR;
R 5 is -hydrogen, -halogen, -alkyl, -cycloalkyl, -heterocycloalkyl, -alkenyl, -cycloalkenyl, -heterocycloalkenyl, -alkynyl, -aryl, -heteroaryl or —[C(R) 2 ] p —XR;
p is 0-10 inclusive;
t is 0-20 inclusive; and
u is 1-20 inclusive.

3. The method of claim 2 , wherein X is absent.

4. The method of claim 2 , wherein R 5 is -hydrogen.

5. The method of claim 2 , wherein W is —SiZ 3 .

6. The method of claim 2 , wherein W is —SR.

7. The method of claim 2 , wherein W is —SiZ 3 ; and Z is —Cl, —Br, or —I.

8. The method of claim 2 , wherein W is —SiZ 3 ; and Z is —Cl.

9. The method of claim 2 , wherein W is —SiZ 3 ; and Z is —OR.

10. The method of claim 2 , wherein W is —SiZ 3 ; Z is —OR; and R is -alkyl.

11. The method of claim 2 , wherein W is —SR.

12. The method of claim 2 , wherein W is —SR; and R is -hydrogen.

13. The method of claim 2 , wherein t is 0-5.

14. The method of claim 2 , wherein u is 1-5.

15. The method of claim 2 , wherein Y is -aryl-.

16. The method of claim 2 , wherein Y is —C 6 H 4 —.

17. The method of claim 2 , wherein said linker is phenyltrichlorosilane.

Assignees

• Gleason Karen K
• Im Sung Gap
• Massachusetts Inst Technology

Inventors

• Gleason Karen K
• Im Sung Gap

Classifications

• C09D165/00

  Coating compositions based on macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain (C09D107/00 - C09D157/00, C09D161/00 take precedence); Coating compositions based on derivatives of such polymers · CPC title

• B05D3/10

  by other chemical means · CPC title

• C09D179/02

  Polyamines · CPC title

• G02F2001/1515

  Physics · mapped topic

• C08G61/125

  with a five-membered ring containing one oxygen atom in the ring · CPC title