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

• US 20050159581A1
• Filed: 10/21/2004
• Published: 07/21/2005
• Est. Priority Date: 10/22/2003
• Status: Active Grant

• 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
• Granted Patent: US 7,259,228 B2
• Time in Patent Office: Days
• US Class Current: 528/391
• 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 polymerisation 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 amine —

NR₁R₂.

3. A method according to claim 2, 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 3, 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 amount of basic compound is between 1 and 2 equivalents with respect to the monomer.

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

8. 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, a phenyl group and a benzyl group, and which may comprise up to 4 heteroatoms selected from the group consisting of oxygen, sulphur, and nitrogen in the aromatic divalent group.

9. 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-anthracenediyl;

2,6-anthracenediyl;

9,10-anthracenediyl;

2,5-thienylene;

2,4-thienylene;

2,3-thienylene;

2,5-furanediyl;

2,5-pyrrolediyl;

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

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

2,5-benzo[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.

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

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

12. 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.

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

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

78 °

C. and 200°

C.

29. A precursor polymer compound having the general formula

30. A precursor polymer compound according to claim 29, wherein R₀ is an amine —

NR₁R₂.

31. A precursor polymer compound according to claim 30, 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.

32. A precursor polymer compound according to claim 31, wherein R₁ and R₂ are independently selected from the group consisting of a methyl group, an ethyl group, a propyl group, a phenyl group and a benzyl group.

33. A precursor polymer compound according to claim 29, 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, a phenyl group and a benzyl group, and which may comprise up to 4 heteroatoms selected from the group consisting of oxygen, sulphur, and nitrogen in the aromatic divalent group.

34. A precursor polymer compound according to claim 29, 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-anthracenediyl;

2,6-anthracenediyl;

9,10-anthracenediyl;

2,5-thienylene;

2,4-thienylene;

2,3-thienylene;

2,5-furanediyl;

2,5-pyrrolediyl;

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

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

2,5-benzo[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.

35. A precursor polymer compound according to claim 29, wherein said precursor polymer has an average molecular weight between 5000 and 1000000 Daltons.

36. A precursor polymer compound according to claim 29, wherein said precursor polymer has a polydispersity between 1.5 and 5.5.

37. A precursor polymer compound according to claim 36, wherein said precursor polymer has a polydispersity below 2.

15. A method according to claim 15, wherein said reacting step is performed at a temperature between −

20°

C. and 30°

C.

16. A method for the preparation of a polymer comprising the structural units

17. A method according to claim 16, wherein providing at least one precursor polymer is performed by providing at least one precursor polymer having the general formula (II) wherein R₀ is an amine —

NR₁R₂.

18. A method according to claim 17, 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.

19. A method according to claim 18, wherein R₁ and R₂ are independently selected from the group consisting of a methyl group, an ethyl group, a propyl group, a phenyl group and a benzyl group.

20. A method according to claim 16, said precursor polymer comprising leaving groups, said leaving groups being eliminated during said conversion step, wherein between 0 and 10% of the leaving groups is not eliminated during said conversion step, thus leading to the formation of a partially converted conjugated polymer.

21. A method according to claim 16, 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-anthracenediyl;

2,6-anthracenediyl;

9,10-anthracenediyl;

2,5-thienylene;

2,4-thienylene;

2,3-thienylene;

2,5-furanediyl;

2,5-pyrrolediyl;

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

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

2,5-benzo[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.

22. A method according to claim 21, wherein said aromatic or heteroaromatic divalent group is 1,4-phenylene or 2,5-thienylene.

23. A method according to claim 22, wherein said aromatic or heteroaromatic divalent group is 2,5 thienylene.

24. A method according to claim 16, wherein R₃ and R₄ are hydrogen.

25. A method according to claim 16, wherein the polymer is a conjugated arylene vinylene polymer.

26. A method according to claim 25, wherein said conjugated arylene vinylene polymer is poly (2,5 thienylene vinylene).

27. A method according to claim 16, wherein said precursor polymer is in the form of a thin film precursor polymer layer and wherein said thermal conversion step is performed under inert atmosphere.

28. A method according to claim 16, wherein said precursor polymer is dissolved in a solvent followed by a degassing step.

38. A conjugated poly(2,5-thienylene vinylene) polymer having the formula:

39. A conjugated poly(2,5-thienylene vinylene) polymer according to claim 38, wherein the average molecular weight is between 5000 daltons and 1000000 daltons.

40. A conjugated poly(2,5-thienylene vinylene) polymer according to claim 38, wherein the polydispersity of the polymer is between 1.5 and 5.5.

41. A device comprising a layer of a conjugated poly(2,5-thienylene vinylene) polymer according to claim 38.

42. A device according to claim 41, wherein said device is a solar cell, a light-emitting diode or an integrated circuit.