Effects of catalyst loading amount on the synthesis of poly(3-hexylthiophene) via externally initiated Kumada catalyst-transfer polycondensation

Abstract

A series of model polymerization are carried out via the one-pot externally initiated Kumada catalyst-transfer polycondensation (KCTP) of 2-bromo-5-chloromagnesium thiophene monomers, and the excess amount of initiators or catalysts are found no need to be isolated during the polycondensation process. Especially, the impacts of the nickel catalyst loading variation on regioregularity (rr), yield, molecular weight (M_n), polydispersity (PDI) and initiation efficiency of poly(3-hexylthiophene) (P3HT) are systematically investigated. The ¹H NMR, size-exclusion chromatography (SEC), and MALDI-TOF mass spectroscopy results indicated that an excess amount of catalyst does not influence yield, rr, M_n, and PDI of P3HT, nor the initiation efficiency. However, the PDI of the product is broad, and the M_n and rr values decreased in the absence of 1,3-bis(diphenylphosphino)propane (dppp). It can be concluded that the in-situ KCTP polymerization of P3HT is a practical and effective process. These results are especially valuable for the synthesis of all-conjugated block copolymers where macroinitiators are used.

Keywords

Kumada catalyst-transfer polycondensation (KCTP) / poly(3-hexylthiophene) (P3HT) / regioregularity (rr)

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Acknowledgements

This work was supported by the Japan Science and Technology Agency (JST), PRESTO program (JY 220176).

RIGHTS & PERMISSIONS

2014 Higher Education Press and Springer-Verlag Berlin Heidelberg