Rapid flow-based synthesis of poly(3-hexylthiophene) using 2-methyltetrahydrofuran as a bio-derived reaction solvent
File(s)
Published version
Accepted version
Author(s)
Bannock, JH
Xu, W
Baïssas, T
Heeney, M
de Mello, JC
Type
Journal Article
Abstract
We report the synthesis of poly(3-hexylthiophene) (P3HT) by Grignard metathesis (GRIM) polymerization using the bio-derived ‘green’ solvent 2-methyltetrahydrofuran (2-MeTHF). Using a standard flask-based reaction, the molecular weight distribution, regioregularity and product yield were found to be similar to those obtained under equivalent conditions using tetrahydrofuran (THF) as a reaction solvent. The synthesis was subsequently adapted to a novel “tube-in-shell” droplet-based flow reactor, using a newly developed high-solubility catalyst derived from nickel(II) bromide ethylene glycol dimethyl ether complex (Ni(dme)Br2) and 1,3-bis(diphenylphosphino)propane (dppp). Use of the new catalyst together with an increased reaction temperature of 65 oC (enabled by the higher boiling point of 2-MeTHF) resulted in an approximate four-fold increase in reaction rate compared to a standard THF- based synthesis at 55 oC, with full conversion reached within one minute. The purified flow- synthesized polymer had an Mw of 46 kg mol-1, a low PDI of 1.4, and a regioregularity of 93 %, indicating the suitability of flow-based GRIM polymerization in 2-MeTHF for the high- throughput synthesis of high quality P3HT.
Date Issued
2016-04-19
Date Acceptance
2016-04-16
Citation
European Polymer Journal, 2016, 80, pp.240-246
ISSN
1873-1945
Publisher
Elsevier
Start Page
240
End Page
246
Journal / Book Title
European Polymer Journal
Volume
80
Copyright Statement
© 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY
license (http://creativecommons.org/licenses/by/4.0/).
license (http://creativecommons.org/licenses/by/4.0/).
License URL
Sponsor
Engineering & Physical Science Research Council (E
Engineering & Physical Science Research Council (EPSRC)
Engineering & Physical Science Research Council (E
Technology Strategy Board
Engineering & Physical Science Research Council (EPSRC)
Engineering and Physical Sciences Research Council
Grant Number
EP/G031088/1
EP/H500227/1
EP/K503733/1
101240
N/A
EP/G037515/1
Subjects
Science & Technology
Physical Sciences
Polymer Science
Semiconducting polymers
Poly(3-hexylthiophene)
P3HT
Flow synthesis
Green synthesis
ORGANIC SOLAR-CELLS
GRIGNARD METATHESIS
POROUS CAPILLARY
DROPLET REACTOR
POLY(3-ALKYLTHIOPHENES)
SEPARATION
EFFICIENCY
CHEMISTRY
IMPACT
Polymers
0303 Macromolecular And Materials Chemistry
0904 Chemical Engineering
0912 Materials Engineering
Publication Status
Published