Externally initiated o-tolyl initiated poly(3-hexylthiophene) (P3HT) was synthesized according to Grignard metathesis polymerization at varying chain length to compare number average molecular weights (Mn) obtained by gel permeation chromatography (GPC) and 1H NMR end group analysis. The extent of overestimation by GPC (1.3) was determined to be lower than previously reported for low Mn polymers. However, an apparent GPC quantification limit was observed as NMR Mn correlated well to predicted results. Static light scattering studies on high Mn polymers provided evidence that the true molecular weight was more similar to GPC-derived Mn. Despite nearly 100% external initiation efficiency, at a certain Mn limit new uninitiated chains may be synthesized. It is suggested that the synthesis of externally initiated P3HT should be limited to Mn below 40 kDa to ensure fully externally initiated chains. A proposal for the synthesis of externally initiated macrocyclic P3HT will also be discussed.

Externally initiated o-tolyl initiated poly(3-hexylthiophene) (P3HT) was synthesized according to Grignard metathesis polymerization at varying chain length to compare number average molecular weights (Mn) obtained by gel permeation chromatography (GPC) and 1H NMR end group analysis. The extent of overestimation by GPC (1.3) was determined to be lower than previously reported for low Mn polymers. However, an apparent GPC quantification limit was observed as NMR Mn correlated well to predicted results. Static light scattering studies on high Mn polymers provided evidence that the true molecular weight was more similar to GPC-derived Mn. Despite nearly 100% external initiation efficiency, at a certain Mn limit new uninitiated chains may be synthesized. It is suggested that the synthesis of externally initiated P3HT should be limited to Mn below 40 kDa to ensure fully externally initiated chains. A proposal for the synthesis of externally initiated macrocyclic P3HT will also be discussed.

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