Process for producing functionalized polythiophenes

Patent metadata

Field	Value
Publication number	US-10767003-B2
Application number	US-201515535920-A
Country	US
Kind code	B2
Filing date	Nov 20, 2015
Priority date	Dec 23, 2014
Publication date	Sep 8, 2020
Grant date	Sep 8, 2020

Abstract

The present invention relates to a process for producing a liquid composition comprising a functionalized π-conjugated polythiophenes, comprising the process steps of i) providing a liquid phase comprising a) thiophene monomers of the general formula (I) wherein X,Y are identical or different and are O, S, or NR1, wherein R1 is hydrogen or an aliphatic or aromatic residue having 1 to 18 carbon atoms; A is organic residue carrying an anionic functional group; b) an oxidizing agent; and c) a solvent; ii) oxidatively polymerizing the thiophene monomers of the general formula (I) to obtain a liquid composition comprising functionalized π-conjugated polythiophenes; wherein (α1) the pH of the liquid phase provided in process step i) is adjusted to a value below 7.0, wherein the pH is determined at a temperature of 20° C.; and (α2) the chloride content of the liquid phase provided in process step i) is less than 10000 ppm, based on the total weight of the liquid phase. The present invention also relates to the liquid composition obtainable by this process, to a liquid composition comprising a functionalized π-conjugated polythiophene, wherein the com-position is characterized by a certain ratio of mass average molecular weight Mw and the molar average molecular weight Mn of the functionalized π-conjugated polythiophene, to a liquid composition comprising a functionalized π-conjugated polythiophene, wherein the functionalized π-conjugated polythiophene comprises different repeating units in a defined amount, to a process for the preparation of such a liquid composition, to a process for the preparation of a capacitor in which these liquid compositions are used for the formation of the solid electrolyte, to a capacitor obtainable by this process and to the use of the liquid compositions for the preparation of a conductive layer.

First claim

The invention claimed is:

1. A process for producing a liquid composition comprising functionalized π-conjugated polythiophenes, the process comprising:
i) providing a liquid phase comprising
a) thiophene monomers of formula (I)

wherein
X and Y are identical or different and are independently selected from O, S, and NR 1 , wherein R 1 is hydrogen or an aliphatic or aromatic residue having 1 to 18 carbon atoms; and
A is an organic residue carrying an anionic functional group;
b) an oxidizing agent; and
c) a solvent;

ii) oxidatively polymerizing the thiophene monomers of formula (I) to obtain the liquid composition;

wherein
(α1) the pH of the liquid phase provided in process step i) is adjusted to a value below 7.0, wherein the pH is determined at a temperature of 20° C.; and
(α2) the chloride content of the liquid phase provided in process step i) is less than 10000 ppm, based on the total weight of the liquid phase.

2. The process according to claim 1 , wherein
(α3) the oxygen content of the liquid phase provided in process step i) is less than 1000 ppm, based on the total weight of the liquid phase.

3. The process according to claim 1 , wherein
X and Y are O, and
A is —(CH 2 ) m —CR 2 R 3 —(CH 2 ) n —,

wherein
R 2 is hydrogen or —(CH 2 ) s —Z—(CH 2 ) p —SO 3 − M + ,
R 3 is —(CH 2 ) s —Z—(CH 2 ) p —SO 3 − M + ,
Z is O, S or —CH 2 —,
M + is a cation,
m and n are identical or different and are independently an integer from 0 to 3,
s is an integer from 0 to 10 and
p is an integer from 1 to 18.

4. The process according to claim 1 , wherein
X and Y are O, and
A is —(CH 2 )—CR 2 R 3 —(CH 2 ) n —,

wherein
R 2 is hydrogen,
R 3 is —(CH 2 ) s —O—(CH 2 ) p —SO 3 − M + ,
M + is Na + or K + ,
n is 0 or 1,
s is 0 or 1, and
p is 4 or 5.

5. The process according to claim 1 , wherein
X and Y are O, and
A is —(CH 2 —CHR)—,

wherein
R is —(CH 2 ) t —O—Ar—[(W) u —SO 3 − M + ] v ,

wherein
Ar is an optionally substituted C 6 -C 20 arylene group;
W is an optionally substituted C 1 -C 6 alkylene group;
M + is H + , an alkali cation selected from the group consisting of Li + , Na + , and K + , NH(R 1 ) 3 or HNC 5 H 5 , wherein each R 1 group is, independently, a hydrogen atom or an optionally substituted C 1 -C 6 alkyl group;
t is an integer of 0 to 6;
u is an integer of 0 or 1; and
v is an integer of 1 to 4.

6. The process according to claim 1 , wherein the oxidizing agent b) is a salt of a heavy metal, a salt of a peroxodisulfate, or a mixture thereof.

7. The process according to claim 1 , wherein the thiophene monomers are polymerized in process step ii) by electrochemical polymerization and wherein the oxidizing agent b) is an electrode.

8. The process according to claim 1 , wherein the solvent c) is water.

9. The process according to claim 1 , wherein the pH of the fluid phase provided in process step i) is adjusted to a value below 7.0 using an organic acid or an inorganic acid.

10. The process according to claim 1 , wherein the oxidative polymerization in process step ii) is performed under an inert gas atmosphere of nitrogen, argon, carbon dioxide or a mixture thereof.

11. The process according to claim 10 , wherein the oxidative polymerization in process step ii) is performed under a pressure that is equal to or above the vapor pressure of the liquid phase during the polymerization reaction in process step ii).

12. The process according to claim 1 , wherein the oxidative polymerization in process step ii) is performed under a reduced pressure of not more than 0.8 bar.

13. A liquid composition obtained by the process according to claim 1 .

14. A liquid composition comprising a functionalized π-conjugated polythiophene, wherein the polythiophene comprises repeating units of formula (I)

wherein
X and Y are both O;
A is an organic residue carrying an anionic functional group; and

wherein the ratio of the mass average molecular weight M w to the molar average molecular weight M n (M w /M n ) of the functionalized π-conjugated polythiophene is at least 6.

15. The liquid composition according to claim 14 , wherein the mass average molecular weight M w of the functionalized π-conjugated polythiophene is at least 50000 g/mol.

16. The liquid composition according to claim 15 , wherein the mass average molecular weight M w of the functionalized π-conjugated polythiophene is in the range from 125000 g/mol to 240000 g/mol.

17. The liquid composition according to claim 14 , wherein the molar average molecular weight M n of the functionalized π-conjugated polythiophene is less than 25000 g/mol.

18. The liquid composition according to claim 14 , wherein the functionalized π-conjugated polythiophene is present in the liquid composition in the form of particles, the particles being characterized by
i) a d 50 -value (weight average particle diameter) in the range from 1 to 100 nm, and
ii) a d 90 -value of less than 3.5×d 50 .

19. A process for producing a liquid composition comprising functionalized π-conjugated polythiophenes, the process comprising:
i) providing a liquid phase comprising
a) thiophene monomers of the general formula (I)

wherein X, Y and A are as defined in claim 1 , and
wherein the liquid phase comprises a mixture of thiophene monomers of formula (Ia) and thiophene monomers of formula (Ib)

and wherein the content of thiophene monomers of formula (Ib) is less than 18 wt.-%, and the content of thiophene monomers of formula (Ia) is more than 82 wt.-%, in each case based on the total weight of the thiophene monomers in the liquid phase, wherein the content of thiophene monomers of formula (Ia) and the content of thiophene monomers of formula (Ib) equal 100 wt.-%;
b) an oxidizing agent; and
c) a solvent; and

ii) oxidatively polymerizing the thiophene monomers of formula (Ia) and (Ib) to obtain the liquid composition.

20. The process according to claim 19 , wherein the content of thiophene monomers of formula (Ib) is at least 0.2 wt.-%, based on the total weight of the thiophene monomers in the liquid phase.

21. A liquid composition obtained by the process according to claim 19 .

22. A liquid composition comprising a functionalized π-conjugated polythiophene, wherein the polythiophene comprises repeating units of formula (I)

wherein
X and Y are identical or different and are independently selected from O, S, and NR 1 , wherein R 1 is hydrogen or an aliphatic or aromatic residue having 1 to 18 carbon atoms; and
A is an organic residue carrying an anionic functional group; and

wherein the functionalized π-conjugated polythiophene comprises repeating units of formula (Ia) and repeating units of formula (Ib)

and wherein the content o

Assignees

• Heraeus Deutschland Gmbh & Co Kg

Inventors

• Scheel Arnulf
• Asteman Katrin
• Intelmann Matthias
• Merker Udo

Classifications

• C25B3/23

  Oxidation (halogenation C25B3/27) · CPC title

• C08G2261/512

  Hole transport · CPC title

• H01B1/127

  comprising five-membered aromatic rings in the main chain, e.g. polypyrroles, polythiophenes · CPC title

• H01G9/028

  Organic semiconducting electrolytes, e.g. TCNQ · CPC title

• C08G2261/794

  with polymeric dopants · CPC title