Surfactant-Free Preparation of Conjugated Polymer Nanoparticles in Aqueous Dispersions Using Sulfate Functionalized Fluorene Monomers

Conjugated polymer nanoparticles (CPNs) can be synthesized by a Suzuki-Miyaura cross-coupling miniemulsion polymerization to give stable dispersions with a high concentration of uniform nanoparticles. However, large amounts of added surfactants are required to stabilize the miniemulsion and prevent the aggregation of the nanoparticles. Removal of the excess surfactant is challenging, and residual surfactant in thin films deposited from these dispersions can reduce the performance of optoelectronic devices. We report a novel approach to prepare stable dispersions with no added surfactant using a fluorene monomer, 2,7-dibromo-9,9-bis(undecanesulfate)-9<i>H</i>-fluorene, with alkyl side chains terminated by negatively charged sulfate groups. This functionality mimics the structure of one of the most commonly used surfactants, sodium dodecyl sulfate (SDS). This charged monomer effectively stabilizes the miniemulsion through electrostatic repulsion without the use of any additional surfactant in molar ratios ranging from 2.0 to 20.0 mol % of total monomer content for the preparation of poly(9,9-dioctylfluorene) (PFO) and poly(9,9-dioctylfluorene-<i>alt</i>-bithiophene) (PF8T2). Incorporation of 5.0 mol % of the amphiphilic monomer gave stable dispersions with a surface potential below -40 mV and, and polymers with molar mass (<i>M</i>_<i>n</i>) above 10 kg mol^-1. This method should be generally applicable to the preparation of dispersions of polyfluorenes for application in organic electronic and optoelectronic devices without the requirement for time-consuming processes to remove residual surfactant.