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Faculty for Biology, Chemistry, and Earth Sciences

Macromolecular Chemistry I:

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Lohwasser, R.H.; Thelakkat, M.: Toward Perfect Control of End Groups and Polydispersity in Poly(3-hexylthiophene) via Catalyst Transfer Polymerization, Macromolecules, 44(9), 3388-–3397 (2011) -- DOI: 10.1021/ma200119s
Abstract:
We report the influence of the active Grignard monomer formation on the end groups and polydispersity of poly(3-hexylthiophene) (P3HT) for the catalyst transfer polymerization. The rate of the active Grignard monomer formation of 2,5-dibromo-3-hexylthiophene using t-BuMgCl was studied using 1H NMR. Only in the absence of unreacted/excess t-BuMgCl, polymers with 100% H/Br end groups were formed. If the active Grignard monomer formation was incomplete and thus unreacted t-BuMgCl remained, the end groups depended on the polymerization time; the ratio of H/Br to H/H end groups decreased with increasing time. LiCl was shown to accelerate the active Grignard monomer formation but negatively affects the regioregularity to a small extent. It also increases the molecular weight of P3HT when used in combination with Ni(dppp)Cl2 as a catalyst. Further, MeOH as a quenching reagent was identified to cause chain−chain coupling and hence an increase in the polydispersity. Thus, important parameters influencing the kinetics of the catalyst transfer polymerization were studied, and a series of P3HTs with 100% H/Br end groups and low polydispersities were synthesized by an optimized procedure. These findings are very relevant for extending this polymerization method to new monomers and for the realization of well-defined block copolymers.
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