Influence of the Carboxylic Acid Additive Structure on the Properties of Poly(3-hexylthiophene) Prepared via Direct Arylation Polymerization (DArP)
Abstract
Carboxylic acids are known to have a profound effect on the rate of direct arylation. Despite this, little attention has been paid to them as additives for direct arylation polymerization (DArP). Here we report the influence of the carboxylic acid chemical structure on the properties of poly(3-hexylthiophene) (P3HT) prepared via DArP. We study the effect that acid pKa, steric bulk, and backbone cyclization have on the reactivity of the DArP catalytic system. We found that pKa values do not correlate with DArP reactivity in the pKa range of 4.76–5.05. The increase of acid size in the classes of linear, secondary, and tertiary acids leads to a continuous increase in polymer yield and molecular weight, whereas for the case of cyclic secondary acids the trend is reversed and a decrease of acid size leads to an increase in polymer yield and molecular weight in an alternating (zigzag) fashion depending on whether the acid contains an even or odd number of carbons. Here, a profound enhancement of reactivity was found for the case of the smallest cyclopropanecarboxylic acid, which yields P3HT with remarkably high molecular weights (Mn 33.4 kDa and Mw 207.1 kDa), which is expected to benefit the development of directmore »
- Authors:
-
- Univ. of Southern California, Los Angeles, CA (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Energy Nanoscience (CEN)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1369887
- Grant/Contract Number:
- SC0001013
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Macromolecules
- Additional Journal Information:
- Journal Volume: 48; Journal Issue: 3; Related Information: CEN partners with University of Southern California (lead); University of Illinois, Urbana-Champaign; University of Michigan; University of Virginia; Journal ID: ISSN 0024-9297
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Organic acids; Organic polymers; Chemical structure; Reactivity; Polymers
Citation Formats
Rudenko, Andrey E., and Thompson, Barry C. Influence of the Carboxylic Acid Additive Structure on the Properties of Poly(3-hexylthiophene) Prepared via Direct Arylation Polymerization (DArP). United States: N. p., 2015.
Web. doi:10.1021/ma502131k.
Rudenko, Andrey E., & Thompson, Barry C. Influence of the Carboxylic Acid Additive Structure on the Properties of Poly(3-hexylthiophene) Prepared via Direct Arylation Polymerization (DArP). United States. https://doi.org/10.1021/ma502131k
Rudenko, Andrey E., and Thompson, Barry C. Thu .
"Influence of the Carboxylic Acid Additive Structure on the Properties of Poly(3-hexylthiophene) Prepared via Direct Arylation Polymerization (DArP)". United States. https://doi.org/10.1021/ma502131k. https://www.osti.gov/servlets/purl/1369887.
@article{osti_1369887,
title = {Influence of the Carboxylic Acid Additive Structure on the Properties of Poly(3-hexylthiophene) Prepared via Direct Arylation Polymerization (DArP)},
author = {Rudenko, Andrey E. and Thompson, Barry C.},
abstractNote = {Carboxylic acids are known to have a profound effect on the rate of direct arylation. Despite this, little attention has been paid to them as additives for direct arylation polymerization (DArP). Here we report the influence of the carboxylic acid chemical structure on the properties of poly(3-hexylthiophene) (P3HT) prepared via DArP. We study the effect that acid pKa, steric bulk, and backbone cyclization have on the reactivity of the DArP catalytic system. We found that pKa values do not correlate with DArP reactivity in the pKa range of 4.76–5.05. The increase of acid size in the classes of linear, secondary, and tertiary acids leads to a continuous increase in polymer yield and molecular weight, whereas for the case of cyclic secondary acids the trend is reversed and a decrease of acid size leads to an increase in polymer yield and molecular weight in an alternating (zigzag) fashion depending on whether the acid contains an even or odd number of carbons. Here, a profound enhancement of reactivity was found for the case of the smallest cyclopropanecarboxylic acid, which yields P3HT with remarkably high molecular weights (Mn 33.4 kDa and Mw 207.1 kDa), which is expected to benefit the development of direct arylation protocols for inherently less reactive substrates.},
doi = {10.1021/ma502131k},
journal = {Macromolecules},
number = 3,
volume = 48,
place = {United States},
year = {Thu Jan 29 00:00:00 EST 2015},
month = {Thu Jan 29 00:00:00 EST 2015}
}
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