Ferrocene cocatalysis for ruthenium-catalyzed radical miniemulsion polymerization

Abstract

In this study we achieved an efficient metal-catalyzed radical “miniemulsion” polymerization with ferrocene (FeCp2) as a cocatalyst in conjunction with a thermoresponsive PEG containing ruthenium catalyst for the polymerization of methacrylate monomers. The iron-cocatalysis worked well even in the miniemulsion similar to homogeneous solution system. The secondary catalytic cycle by ferrocene allows regeneration of Ru(II) activator species through reduction of accumulated Ru(III) deactivator as well as promotion of halogen-capping or deactivation for the active radical species. The effectiveness of this iron cocatalyst in miniemulsion was investigated with both higher polymerization rate and reaching conversion (>90%) than without FeCp2. In this system, the halogen counterion on the cationic surfactant was a major factor in determining the polymerization rate and the end group fidelity. Interestingly, when a non-ionic surfactant was used for the FeCp2-cocatalyzed miniemulsion, a simple addition of salt carrying common halogen ion (e.g., NaCl) in aqueous phase was very effective in terms of polymerization control.