Fluorine-rich block copolymers (BCPs) are applied in a variety of fields ranging from medicine to optics. However, it is difficult to synthesize well-defined fluorine-rich BCPs because blocks bearing long perfluoroalkyl chains have both hydrophobicity and lipophobicity, resulting in severe lack of solubility. Herein, we report the synthesis and self-assembly behavior of fluorine-rich BCPs prepared from norbornene monomers bearing perfluoroalkyl chains through the controlled ring-opening metathesis polymerization (ROMP) using Grubbs 3<sup>rd</sup> catalyst and their micelle formation. We first prepared the first block with a norbornene monomer with high solubility in solvent, followed by the addition of a second norbornene monomer bearing fluorine moieties. Due to the low solubility of the fluorine-rich block, the BCPs undergo the in-situ self-assembly during polymerization, yielding micelles in solution. The packing parameter increases like typical polymeric micelles when the degree of polymerization for the fluorous norbornene block is increased. We also observe the morphology of micelles can be further modified by the introduction of a small volume fraction of fluorous solvents. The size of fluorous BCP micelles decreases as time elapses and eventually reach the equilibrium structure.

Synthesis of fluorine-rich block copolymers through ring-opening metathesis polymerization and their <i>in-situ</i> micellization behavior in solution

254th National Meeting (2017)

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Synthesis of fluorine-rich block copolymers through ring-opening metathesis polymerization and their in-situ micellization behavior in solution