Processes for purifying diketopyrrolopyrrole copolymers

Patent metadata

Field	Value
Publication number	US-9399698-B2
Application number	US-201414169415-A
Country	US
Kind code	B2
Filing date	Jan 31, 2014
Priority date	Jan 31, 2014
Publication date	Jul 26, 2016
Grant date	Jul 26, 2016

Abstract

Processes for purifying diketopyrrolopyrrole (DPP) copolymers are disclosed. An organic phase containing the DPP copolymer is treated with an aqueous ammonia solution and then with a palladium scavenger. The DPP copolymer is then isolated, and has a very low palladium content. The resulting DPP copolymer has high mobility.

First claim

The invention claimed is:

1. A process for obtaining a diketopyrrolopyrrole copolymer having low palladium content, comprising:
receiving an organic phase containing the diketopyrrolopyrrole copolymer;
treating the organic phase with an aqueous ammonia solution at a tempature of from about 50° C. to about 80° C.;
treating the organic phase with a palladium scavenger; and
isolating the diketopyrrolopyrrole copolymer from the organic phase to obtain the diketopyrrolopyrrole copolymer having low palladium content.

2. The process of claim 1 , wherein the diketopyrrolopyrrole copolymer has a palladium content of less than 150 ppm and a total metal content of less than 300 ppm.

3. The process of claim 1 , wherein the diketopyrrolopyrrole copolymer having low palladium content has a weight average molecular weight of 20,000 or higher when measured using high-temperature gel permeation chromatography in trichlorobenzene at 140° C.

4. The process of claim 1 , wherein the diketopyrrolopyrrole copolymer having low palladium content has a polydispersity index (PDI) of less than 4.0.

5. The process of claim 1 , wherein the organic phase includes an organic solvent selected from the group consisting of anisole, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene, trimethylbenzene, mesitylene, tetrahydronapthalene, and mixtures thereof.

6. The process of claim 1 , wherein the palladium scavenger is sodium diethyldithiocarbamate, ethylenediamine tetraacetic acid (EDTA), or ethylene diamine.

7. The process of claim 1 , wherein the palladium scavenger is a polymer containing a monomer selected from the group consisting of styryl sulfonic acid, vinyl pyridine, styryl thiol, and mercaptoethyl acrylate; or wherein the palladium scavenger includes a functional group selected from the group consisting of thiourea, benzyl amine, imidazolylalkyl, aminoalkyl, thioalkyl, imidazolylalkyl amino, mercaptophenyl amino, and aminoethyl amino.

8. The process of claim 1 , wherein the aqueous ammonia solution contains from about 2% to about 30% ammonia (v/v).

9. The process of claim 1 , wherein the organic phase is treated with the aqueous ammonia solution for a time period of 30 minutes to 90 minutes.

10. The process of claim 1 , wherein the diketopyrrolopyrrole copolymer is isolated from the organic phase by extraction, precipitation, and vacuum filtration.

11. The process of claim 1 , wherein the organic phase containing the diketopyrrolopyrrole copolymer is prepared by:
reacting a reaction mixture that contains a diketopyrrolopyrrole monomer, an aryl comonomer, a palladium catalyst, an organic phase, and an aqueous phase, so that the diketopyrrolopyrrole copolymer is formed; and
separating the organic phase containing the diketopyrrolopyrrole copolymer from the reaction mixture.

12. The process of claim 11 , wherein the reacting occurs at a temperature of from 60° C. to 120° C.

13. The process of claim 11 , wherein the reacting occurs for a time period of from about 6 hours to about 36 hours.

14. The process of claim 11 , wherein the palladium catalyst is present in the amount of from about 1 mole % to about 5 mole % of the reaction mixture.

15. The process of claim 11 , wherein the aqueous phase contains from 1 to 10 molar equivalents of a base, and wherein the volume ratio of organic phase to aqueous phase in the reaction mixture is from about 1:1 to about 5:1.

16. The process of claim 11 , wherein the diketopyrrolopyrrole monomer has the structure of Formula (I):

wherein Ar 1 and Ar 2 are independently aryl, substituted aryl, heteroaryl, or substituted heteroaryl;
R 1 and R 2 are independently hydrogen, alkyl, substituted alkyl, poly(ethylene glycol), poly(propylene glycol), aryl, substituted aryl, heteroaryl, or substituted heteroaryl; and
Y 1 and Y 2 are independently halogen.

17. The process of claim 16 , wherein Ar 1 and Ar 2 are independently selected from the group consisting of thiophene, furan, thienothiophene, and selenophene.

18. The process of claim 11 , wherein the aryl comonomer is an aryl boronate having the structure of Formula (III):
BE-Ar″—BE  Formula (III)

wherein BE is selected from the group consisting of:

and wherein Ar″ is selected from the group consisting of:

wherein each R′ is independently selected from hydrogen, alkyl, substituted alkyl, poly(ethylene glycol), poly(propylene glycol), aryl, substituted aryl, heteroaryl, substituted heteroaryl, halogen, alkoxy, alkylthio, trialkylsilyl, —CN, or —NO 2 ; and X is C or Si.

19. The process of claim 11 , wherein the palladium catalyst has the structure of Formula (IV):

wherein R a is H, —N(CH 3 ) 2 , or —CF 3 .

20. The process of claim 19 , wherein R a is —N(CH 3 ) 2 .

Assignees

• Xerox Corp

Inventors

• Wigglesworth Anthony James
• Wu Yiliang
• Vong Cuong

Classifications

• C08G2261/1412

  Saturated aliphatic units · CPC title

• C08G2261/3221

  containing one or more nitrogen atoms as the only heteroatom, e.g. pyrrole, pyridine or triazole · CPC title

• C08G2261/92

  TFT applications · CPC title

• C08G2261/12

  Copolymers · CPC title

• C08G2261/3223

  containing one or more sulfur atoms as the only heteroatom, e.g. thiophene · CPC title