Method for fabricating an aromatic polymer and a polymer fabricated according thereto

Patent metadata

Field	Value
Publication number	US-12258668-B2
Application number	US-202318337743-A
Country	US
Kind code	B2
Filing date	Jun 20, 2023
Priority date	Jun 20, 2023
Publication date	Mar 25, 2025
Grant date	Mar 25, 2025

Abstract

A method for fabricating a chemical composition containing an aromatic polymer, including the steps of: providing an anodic region and a cathodic region; providing an arene precursor; providing an electrochemical potential between the anodic region and the cathodic region; reacting the arene precursor via the electrochemical potential to form the composition, which further includes the step of conducting a cathodic reaction. A chemical composition containing an aromatic polymer prepared according to the method.

First claim

We claim:

1. A method for fabricating a chemical composition comprising an aromatic polymer, comprising the steps of:
a) providing an anodic region and a cathodic region;
b) providing an arene precursor, wherein the arene precursor is selected from the group consisting of a phenyl halide, a halogenated polycyclic aromatic hydrocarbon, and a combination thereof, and wherein the arene precursor comprises more than one halogen;
c) providing an electrochemical potential between the anodic region and the cathodic region;
d) reacting the arene precursor under mild conditions with neither organometallic, metallic nor base catalyst via the electrochemical potential to form the chemical composition, wherein the reacting step d) further comprises the step of conducting a cathodic reaction.

2. The method according to claim 1 , wherein the cathodic reaction further comprises the step of conducting a dehalogenation coupling reaction of the arene precursor to form the chemical composition.

3. The method according to claim 2 , wherein the reacting step d) further comprises the step of forming the arene precursor into a halogenated radical as an intermediate to further form the chemical composition.

4. The method according to claim 2 , wherein the dehalogenation coupling reaction is conducted under constant voltage of from about 1.5V to about 3.5V for from about 2 hours to about 36 hours at a temperature of from about 0° C. to about 60° C.

5. The method according to claim 4 , wherein the electrolyte comprises tetrabutylammonium hexafluorophosphate at a concentration of from about 0.05 mmol/mL to about 1 mmol/mL, and wherein the arene precursor concentration is from about 0.001 mmol/mL to about 0.5 mmol/mL.

6. The method according to claim 1 , wherein the method further comprising the step of providing an anodic electrode at the anodic region, a cathodic electrode at the cathodic region, and a solution comprising an electrolyte, wherein the anodic electrode and the cathodic electrode are at least partially contacting the solution.

7. The method according to claim 6 , wherein the reacting step d) further comprises the step of simultaneously polymerizing the arene precursor to form the chemical composition and forming a film of the chemical composition on a surface of the cathodic electrode.

8. The method according to claim 6 , wherein the electrolyte is selected from the group consisting of: hexafluorophosphates, tetrafluoroborates, ammonium bromides, perchlorate, and a combination thereof, optionally the electrolyte is selected from the group consisting of: tetramethylammonium hexafluorophosphate (TMAPF 6 ), tetraethylammonium hexafluorophosphate (TEAPF 6 ), tetrabutylammonium hexafluorophosphate (TBAPF 6 ), potassium hexafluorophosphate (KPF 6 ), tetramethylammonium tetrafluoroborates (TMABF 4 ), tetraethylammonium tetrafluoroborates (TEABF 4 ), tetrabutylammonium tetrafluoroborates (TBABF 4 ), potassium tetrafluoroborates (KBF 4 ), lithium perchlorate (LiClO 4 ), and a combination thereof.

9. The method according to claim 6 , wherein the solution further comprises a solvent; optionally, wherein the solvent comprises an anhydrous organic solvent; optionally, the solvent is selected from the group consisting of: acetone, acetonitrile, toluene, dichloromethane, chloroform, tetrahydrofuran, dimethylformamide, dimethyl sulfoxide, benzonitrile, and a combination thereof.

10. The method according to claim 9 , wherein the solvent comprises acetonitrile and toluene; optionally, wherein the ratio of acetonitrile to toluene is from about 8:1 to about 2:1; optionally the ratio of acetonitrile to toluene is about 4:1.

11. The method according to claim 6 , wherein the anodic electrode comprises a conductive substrate; preferably wherein the substrate comprises an inert conductive metal selected from the group consisting of platinum, titanium, an alloy thereof, and a combination thereof.

12. The method according to claim 6 , wherein the cathodic electrode comprises a conductive substrate selected from the group consisting of silicon, gold, platinum, stainless steel, an alloy thereof, and a combination thereof.

13. The method according to claim 1 , wherein the aromatic polymer is a conjugated polymer; optionally, the aromatic polymer is an unsubstituted conjugated polymer.

14. The method according to claim 1 , wherein the aromatic polymer takes a form selected from the group consisting of a dimeric form, an oligomeric form, a polymeric form, and a combination thereof.

15. The method according to claim 1 , the halogen is selected from the group consisting of a fluorine, a chlorine, a bromine, an iodine, and a combination thereof, preferably, the halogen comprises a bromine or an iodine.

16. The method according to claim 1 , wherein the arene precursor is a dihaloarene, optionally, the arene precursor is selected from the group consisting of: dihalobenzene, dihalonaphthalene, dihalobiphenyl, dihaloanthracene, dihalophenanthrene, dihalophenalene, dihalopyrene, diphenylbenzene, dihalonaphthacene, dihalotriphenylene, dihalochrysene, dihalobenzo[c]phenanthrene, dihalobenz[a]anthracene, and a combination thereof.

17. The method according to claim 16 , wherein the arene precursor comprises a first halogen and a second halogen, wherein the second halogen is located on the precursor substantially opposite the first halogen, and wherein a first dehalogenation reaction takes place at the first halogen and a second dehalogenation reaction takes place at the second halogen.

18. The method according to claim 1 , wherein the aromatic polymer forms a covalent organic framework.

19. The method according to claim 18 , wherein the arene precursor is a trihaloarene; optionally, wherein the arene precursor is selected from the group consisting of: 1,3,5-trihalobenzene, 1,3,5-tris(4-halophenyl)benzene and a combination thereof.

20. The method according to claim 18 , wherein the arene precursor is a tetrahaloarene, optionally, wherein the arene precursor comprises a 1,3,6,8-tetrahalopyrene.

21. The method according to claim 1 , wherein the arene precursor is a dihaloarene or a trihaloarene, and wherein two or three halogens substitute respective hydrogens at positions of the same arene precursor so that their distance(s) between each other are the greatest.

22. The method according to claim 1 , wherein the arene precursor comprises at least two different precursors.

23. The method according to claim 1 , wherein the step b) of providing the arene precursor further comprises the step of adding the arene precursor into the cathodic region, wherein the cathodic region is separate from the anodic region.

24. The method according to claim 1 , further comprising, after the reacting step d) the step of adding a quenching agent for quenching of the reactions; optionally, the quenching agent is selected from the group consisting of: water, a salt solution and the solvent, and a combination thereof.

25. The method according to claim 1 , further comprising, after the reacting step d) the step of reversing positive and negative poles of the electrochemical potential for quenching of the reactions.

26. The method according to claim 1 , further comprising, after the reacting step d), the step of f) washing the composition with a washing agent selected from the group consisting of water, ethanol, methanol, n-hexane, 2-dichlorobenzene, dichloromethane, 1,2-dichloroethane, tetrahydr

Assignees

• Univ City Hong Kong

Inventors

• Zhang Qichun
• Wang Xiang

Classifications

• C25B3/29

  Coupling reactions · CPC title

• C08G61/10

  only aromatic carbon atoms, e.g. polyphenylenes · CPC title

• C08G61/02

  Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes · CPC title

• C08G2261/44

  Electrochemical polymerisation, i.e. oxidative or reductive coupling · CPC title

• C25B3/01

  Products · CPC title