Synthesis of Narrowly Distributed α,ω-Bifunctionalized Conjugated Polymers

End-functional conjugated polymers are generally synthesized with stoichiometric-biased monomer combinations in conventional step growth polymerizations (SGPs), which lead to broad species distribution and difficult-to-control end functionality of the polymeric products due to the uncontrolled nature of the method employed. To overcome such disadvantages, a general controlled method was developed for the synthesis of narrowly distributed end-functional conjugated polymers with high-end functionality purity and a predefined molecular weight. This strategy relies on the spatial confinement effect of the nanoreactors, whereby polymeric species with higher molecular weight have a lower chance of further involvement in SGP. Numerical calculations on the kinetic equations demonstrated the formation of narrowly distributed polymers with a high degree of chain-end functionalization. Experimental results based on various analysis methods confirmed the controlled synthesis of bifunctionalized poly(p-phenylene)s with high-end functionality purity and low dispersity value down to 1.06.