Chain-growth cationic polymerization of 2-halogenated thiophenes promoted by Brønsted acids

Literature Information

Publication Date 2014-06-16
DOI 10.1039/C4PY00521J
Impact Factor 5.582
Authors

Arumugam Balasubramanian, Ting-Chia Ku, Hong-Pin Shih, Alishetty Suman, Huang-Jyun Lin, Ting-Wen Shih, Chien-Chung Han


View Original

Abstract

Brønsted acids are found to be effective and generally applicable catalysts for inducing the cationic chain-growth polymerization of a wide variety of 2-halogenated-3-substituted-thiophenes with hydrogen, alkyl, alkylthio, alkoxy, and dialkoxy substituent groups. The effectiveness of the cationic polymerization depends on the acid strength and the electron density of the 2-halothiophene monomer. For the most electron-rich monomer, like EDOT, the polymerization can be initiated essentially with any acid that is stronger than acetic acid. While for the electron-poor 2-bromothiophene, it only works with the strongest acid, e.g., trifluoromethanesulfonic acid. Using this new polymerization method, highly solution-processable and conductive poly(alkylthiothiophene)s with a conductivity greater than 180 S cm−1 can be conveniently prepared. Control experiments indicate that Lewis acid like BF3 and SnCl4 (0.5 equiv.) can also induce the polymerization of 3-alkylthio-2-bromothiophenes in a similar fashion, but their polymerization failed totally in the presence of a trace amount of acid scavenger (e.g., <0.1 equiv. NEt3). On the other hand, similar polymerizations with Brønsted acid did not show any noticeable adverse effect under the same condition. The polymerization with Brønsted acid may involve the coupling between the monomer (as the nucleophile) and its protonated form (as the electrophile), followed by the elimination of HBr (or HCl) to convert the unstable nonconjugated dimeric intermediate 11 (Scheme 2) into the more stable conjugated chain growing species 12, which then initiates the polymerization by repeating the propagation steps of coupling with additional monomers, and then undergoes HX-elimination to regenerate the chain-growing centres.

Related Literature

Structural and spectroscopic characterization of potassium fluoroborohydrides

Richard H. Heyn, Ivan Saldan, Magnus H. Sørby, Christoph Frommen, Bjørnar Arstad, Aud M. Bougza, Helmer Fjellvåg, Bjørn C. Hauback

2013-05-17 Communication

DOI: 10.1039/C3CP52070F

Chromism based on supramolecular H-bonds

Chuanlang Zhan, Xunlei Ding, Shanlin Zhang, Xin Zhang, Huiying Liu, Lili Chen, Yishi Wu, Hongbing Fu, Shenggui He, Yan Huang, Jiannian Yao

2013-05-20 Paper

DOI: 10.1039/C3CP51268A

Inside front cover

Cover

DOI: 10.1039/C3CP90111D

Luminescence spectroscopy of singlet oxygen enables monitoring of oxygen consumption in biological systems consisting of fatty acids

Anita Gollmer, Johannes Regensburger, Tim Maisch, Wolfgang Bäumler

2013-05-14 Paper

DOI: 10.1039/C3CP50841B

Superoxide generation from the reduction of oxygen at the carbon–oil–water triple phase boundary

Rita Nissim, Richard G. Compton

2013-06-05 Paper

DOI: 10.1039/C3CP51732B

Enantiotopic discrimination and director organization in the twist-bend nematic phase

Cristina Greco, Geoffrey R. Luckhurst, Alberta Ferrarini

2013-07-18 Communication

DOI: 10.1039/C3CP52222A

Front cover

Cover

DOI: 10.1039/C3CP90084C

Multidimensional local mode calculations for the vibrational spectra of OH−(H2O)2 and OH−(H2O)2·Ar

Masato Morita, Kaito Takahashi

2013-07-01 Paper

DOI: 10.1039/C3CP51903A

You might also like

Compound Q&A

Are there alternatives to 1-(4-Chlorophenyl)-N-hydroxymethanimine (CAS: 3848-36-0) in synthesis?

When considering alternatives to 1-(4-Chlorophenyl)-N-hydroxymethanimine (CAS: 3...

3848-36-01-(4-Chlorophenyl)-N...
Compound Q&A

How is 3-(4-Bromophenyl)-5-(2-fluorophenyl)-1,2,4-oxadiazole (CAS: 419553-16-5) typically synthesized?

3-(4-Bromophenyl)-5-(2-fluorophenyl)-1,2,4-oxadiazole is synthesized through a m...

419553-16-53-(4-Bromophenyl)-5-...
Compound Q&A

How is 5-Chloro-2-(4-chlorophenyl)-4-methyl-6-[3-(1-piperidinyl)propoxy]pyrimidine (CAS: 1639220-19-1) typically synthesized?

5-Chloro-2-(4-chlorophenyl)-4-methyl-6-[3-(1-piperidinyl)propoxy]pyrimidine (CAS...

1639220-19-15-Chloro-2-(4-chloro...
Compound Q&A

What industries use 2-Chloro-4-(difluoromethoxy)pyridine (CAS: 1206978-15-5)?

2-Chloro-4-(difluoromethoxy)pyridine is used in the pharmaceutical industry for ...

1206978-15-52-Chloro-4-(difluoro...
Compound Q&A

What regulatory guidelines apply to 3-Chloro-6-methylpyridazine (CAS: 1121-79-5)?

3-Chloro-6-methylpyridazine (CAS: 1121-79-5) is classified under the Globally Ha...

1121-79-53-Chloro-6-methylpyr...
Compound Q&A

Are there alternatives to Methyl 4,5-dimethyl-2-nitrobenzoate in synthesis?

Several alternatives can be used in the synthesis of Methyl 4,5-dimethyl-2-nitro...

90922-74-0Methyl 4,5-dimethyl-...
Compound Q&A

Are there alternatives to (2E,2'E)-3,3'-(1,4-Phenylene)bisacrylaldehyde in synthesis?

Alternatives to (2E,2'E)-3,3'-(1,4-Phenylene)bisacrylaldehyde include other acry...

63405-68-5(2E,2'E)-3,3'-(1,4-P...
Compound Q&A

What is 3-Amino-5-chloropyridin-2-ol hydrochloride (CAS: 1261906-29-9)?

3-Amino-5-chloropyridin-2-ol hydrochloride is an organic compound with the CAS n...

1261906-29-93-Amino-5-chloropyri...
Compound Q&A

What precautions should be taken when handling 6,7-Difluoro-2,3-dihydro-4H-chromen-4-one (CAS: 1092349-93-3)?

When handling 6,7-Difluoro-2,3-dihydro-4H-chromen-4-one, it is essential to wear...

1092349-93-36,7-Difluoro-2,3-dih...

Source Journal

Polymer Chemistry

Polymer Chemistry
CiteScore: 8.6
Self-citation Rate: 7.3%
Articles per Year: 457

Polymer Chemistry welcomes submissions in all areas of polymer science that have a strong focus on macromolecular chemistry. Manuscripts may cover a broad range of fields, yet no direct application focus is required.

Recommended Compounds

Recommended Suppliers

Disclaimer
This page provides academic journal information for reference and research purposes only. We are not affiliated with any journal publishers and do not handle publication submissions. For publication-related inquiries, please contact the respective journal publishers directly.
If you notice any inaccuracies in the information displayed, please contact us at support@chemtradehub.com. We will promptly review and address your concerns.