Synthesis of functionalizable or functionalized poly(3,4-ethylenedioxythiphene)-based polymers and monomers therefor

Patent metadata

Field	Value
Publication number	US-11180507-B2
Application number	US-201716315954-A
Country	US
Kind code	B2
Filing date	Jul 10, 2017
Priority date	Jul 8, 2016
Publication date	Nov 23, 2021
Grant date	Nov 23, 2021

Abstract

A method of forming a compound having the formula (I′): (I′) includes the reaction: (II′) in the presence of a base, wherein X is a halo atom selected from the group consisting of Cl, Br and I.

First claim

What is claimed is:

1. A method of forming a monomer:

comprising, the reaction:

in the presence of a base which is potassium tert-butoxide in a single reaction vessel at room temperature and a reaction time of 30 minutes to achieve a yield of at least 95% with quantitative conversion, wherein X is a halo atom selected from the group consisting of Cl, Br and I.

2. The method of claim 1 wherein the reaction takes place under conditions to limit nucleophilic addition reactions by the base.

3. The method of claim 1 wherein the reaction yield is approximately 100%.

4. The method of claim 1 wherein X is Cl.

5. A method of forming a polymer, comprising:
forming exomethylene functionalized 3,4-ethylenedioxythiophene monomer having the formula:

via the reaction:

in the presence of a base which is potassium tert-butoxide in a single reaction vessel at room temperature and a reaction time of 30 minutes to achieve a yield of at least 95% with quantitative conversion, wherein X is a halo atom selected from the group consisting of Cl, Br and I; and
polymerizing monomers comprising at least one of the exomethylene functionalized 3,4-ethylenedioxythiophene monomer or a reaction product of the exomethylene functionalized 3,4-ethylenedioxythiophene monomer and a compound including a group reactive with the exomethylene group of the exomethylene functionalized 3,4-ethylenedioxythiophene monomer via a polymerization reaction, wherein the monomers have a purity of at least 95% in the polymerization reaction.

6. The method claim 5 wherein the polymerization reaction is an electropolymerization reaction and the method further comprises functionalization of the polymer after synthesis by reacting with a compound including a group reactive with the exomethylene group of the exomethylene functionalized 3,4-ethylenedioxythiophene.

7. The method of claim 5 wherein the monomers have a concentration of at least 20 mM in the polymerization reaction.

8. The method of claim 5 wherein the group reactive with the exomethylene group is a thiol group.

9. The method of claim 5 wherein the compound including the group reactive with the exomethylene group is selected from the group consisting of 3-mercaptopropionic acid, 3-Chloro-1-propanethiol, 1-mercapto-2-propanol, 3-mercapto-1-propanol, 3-amino-1-propanethiol hydrochloride, 4-mercapto-1-butano, 6-mercaptohexanoic acid, 6-mercapto-1-hexanol, 6-mercapto-1-hexanol, 6-amino-1-hexanethiol hydrochloride, 8-mercaptooctanoic acid, 8-mercapto-1-octanol, 8-amino-1-octanethiol hydrochloride, 9-mercapto-1-nonanol, 11-mercaptoundecanoic acid, 11-mercaptoundecanamide, 11-azido-1-undecanethiol, 11-mercapto-1-undecanol, 11-amino-1-undecanethiol hydrochloride, 11-mercaptoundecylphosphonic acid, 11-mercaptoundecylphosphoric acid, 12-mercaptododecanoic acid, 1-(11-mercaptoundecyl)imidazole, (11-mercaptoundecyl)-N,N,N-trimethylammonium bromide, 11-(1H-pyrrol-1-yl)undecane-1-thiol, 6-(ferrocenyl)hexanethiol, 12-mercaptododecanoic acid NHS ester, 16-mercaptohexadecanoic acid, 16-mercaptohexadecanamide, 16-amino-1-hexadecanethiol hydrochloride, 11-mercaptoundecyl hydroquinone, triethylene glycol mono-11-mercaptoundecyl ether, (11-mercaptoundecyl)tetra(ethylene glycol), 11-(ferrocenyl)undecanethiol, (11-mercaptoundecyl)hexa(ethylene glycol), or a biomolecule.

10. The method of claim 9 wherein the biomolecule is a zwitterionic amino acid cysteine, a peptide, a protein, or a nucleic acid.

Assignees

• Univ Pittsburgh Commonwealth Sys Higher Education
• Univ Of Pittsburgh—Of The Commonwealth System Of Higher Education

Inventors

• Cui Xinyan
• Cao Bin

Classifications

• Y02E10/549

  Organic PV cells · CPC title

• C08F2400/02

  Control or adjustment of polymerization parameters · CPC title

• C08F28/06

  by a heterocyclic ring containing sulfur · CPC title

• C07D495/04 Primary

  Ortho-condensed systems · CPC title

• C08F2/58

  Polymerisation initiated by direct application of electric current (electrolytic processes, e.g. electrophoresis C25) · CPC title