Method of preparing derivatives of polyarylene vinylene and method of preparing an electronic device including same

• US 7,259,228 B2
• Filed: 10/21/2004
• Issued: 08/21/2007
• Est. Priority Date: 10/22/2003
• Status: Expired due to Fees

• Current Assignee: Interuniversitair Micro-Electronica Centrum VZW (IMEC International), Limburgs Universitair Centrum
• Original Assignee: Interuniversitair Micro-Electronica Centrum VZW (IMEC International), Limburgs Universitair Centrum
• Inventors: Lutsen, Laurence, Vanderzande, Dirk, Henckens, Anja, Colladet, Kristof
• Primary Examiner(s): Truong; Duc
• Application Number:
  US10/971,784
• Publication Number:
  US 20050159581A1
• Time in Patent Office: 1,034 Days
• Field of Search: 528/390, 528/391, 528/373, 528/377, 528/489, 528/503, 528/492, 428/690, 428/917
• US Class Current: 528/390
• CPC Class Codes: C08F 126/06 by a heterocyclic ring containing nitrogen
• CPC Class Codes: C08F 128/06 by a heterocyclic ring containing sulfur
• CPC Class Codes: C08F 228/02 by a bond to sulfur
• CPC Class Codes: C08F 28/02 by a bond to sulfur
• CPC Class Codes: C08F 28/06 by a heterocyclic ring containing sulfur
• CPC Class Codes: C08F 290/14 Polymers provided for in subclass C08G
• CPC Class Codes: C08G 61/02 Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
• CPC Class Codes: C08G 61/12 Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
• CPC Class Codes: C08G 61/126 with a five-membered ring containing one sulfur atom in the ring
• CPC Class Codes: H10K 85/111 comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
• CPC Class Codes: H10K 85/114 Poly-phenylenevinylene; Derivatives thereof
• CPC Class Codes: Y02E 10/549 Organic PV cells
• CPC Class Codes: Y10S 428/917 Electroluminescent

Abstract

A technique is described for the preparation of polymers according to a process in which the starting compound of formula (I) is polymerized in the presence of a base in an organic solvent. No end chain controlling agents are required during the polymerization to obtain soluble precursor polymers. The precursor polymer such obtained comprises structural units of the formula (II). In a next step, the precursor polymer (II) is subjected to a conversion reaction towards a soluble or insoluble conjugated polymer by thermal treatment. The arylene or heteroarylene polymer comprises structural units of the formula III. In this process the dithiocarbamate group acts as a leaving group and permits the formation of a precursor polymer of structural formula (II), which has an average molecular weight from 5000 to 1000000 Dalton and is soluble in common organic solvents. The precursor polymer with structural units of formula (II) is thermally converted to the conjugated polymer with structural formula (III)

Claims

1. A method for the preparation of a precursor polymer having the general formula:

2. A method according to claim 1, wherein providing a monomer is performed by providing a monomer with general formula (I) wherein R₀ is an amino group —

NR₁R₂.

3. A method according to claim 1, wherein R₀ is an amino group —

NR₁R₂. and wherein R₁ and R₂ are independently from each other an organic group selected from the group consisting of a C₁-C₂₀-alkyl group, a cyclic C₃-C₂₀-alkyl group, an aryl group, an alkylaryl group, an arylalkyl group and a heterocyclic group.

4. A method according to claim 1, wherein R₀ is an amino group —

NR₁R₂, and wherein R₁ and R₂ are independently selected from the group consisting of a methyl group, an ethyl group, an isopropyl group, a phenyl group and a benzyl group.

5. A method according to claim 1 wherein said basic compound is selected from the group consisting of a metal hydride, a metal alkoxide, a metal hydroxide, a metal amide, a metal amine, an organometal compound wherein the metal is an alkali metal or alkali earth metal, a grignard reagent, ammonium hydroxide, pyridine and phosphazene bases.

6. A method according to claim 1, wherein the concentration of monomer (I) is between 0.1 M and 0.3 M.

7. A method according to claim 1, wherein the Ar is an aromatic divalent group with 4 to 20 carbon atoms which may be substituted with one or more substituents independently selected from the group consisting of C₁-C₂₀-alkyl, C₃-C₂₀-alkoxy, C₁-C₂₀-alkylsulfate, selected from the group consisting of oxygen, sulphur, and nitrogen in the aromatic divalent group.

8. A method according to claim 1, wherein said aromatic or heteroaromatic divalent group is selected from the group consisting of 1,4-phenylene;

2,6-naphthalenediyl;

1,4-naphthalenediyl;

1,4-antbracenediyl;

2,6-anthracenediyl;

9,10-anthracenediyl;

2,5-thienylene;

2,4-thienylene;

2,3-thienylene;

2,5-furanedlyl;

2,5-pyrroledlyl;

1,3,4-oxadiazole-2,5-diyl;

1,3,4-thiadiazole-2,5-diyl;

2,5benzo[c]thienylene;

thieno[3,2-b]thiophene-2,5-diyl;

pyrrolo[3,2-b]pyrrole-2,5-diyl;

pyrene-2,7-diyl;

4,5,9,10-tetrahydropyrene-2,7-diyl;

4,4′

-bi-phenylene;

phenantrene-2,7-diyl;

9,10-dihydrophenantrene-2,7-diyl;

dibenzofurane-2,7-diyl;

dibenzothiophene-2,7-diyl.

9. A method according to claim 8, wherein said aromatic or heteroaromatic divalent group is 1,4-phenylene or 2,5-thienylene.

10. A method according to claim 9, wherein said aromatic or heteroaromatic divalent group is 2,5 thienylene.

11. A method according to claim 4, wherein R₁ and R₂ are independently from each other selected from the group consisting of methyl, ethyl and isopropyl.

12. A method according to claim 1, wherein said organic solvent is an aprotic solvent.

13. A method according to claim 1, wherein said reacting step is performed at a temperature between −

78°

C. and 200°

C.

14. A method according to claim 1, wherein said reacting step is performed at a temperature between −

20°

C. and 30°

C.