In this work, a new emulsion polymerization based on Activators Regenerated by Electron Transport (ARGET ATRP) was developed to produce poly(methyl methacrylate) (PMMA). Mini monomer encapsulated (Mini ME) ARGET ATRP emulsion polymerization resulted in well-defined PMMA with a dispersity as low as 1.14. By localizing the propagation and controlling the availability of the monomer, we provide a foundation that addresses the challenges of traditional miniemulsion and emulsion polymerizations. In this method, monomer is isolated in a micelle by pre-emulsification through high-power stirring. Acetone is introduced to the polymerization to aid in reactant transport and tetrabutylammonium salts, for example, tetrabutylammonium bromide (TBAB) and tetrabutylammonium chloride (TBAC), are used as phase transfer agents. ATRP components such as ATRP catalyst, ligand, TBAB/TBAC, and initiator are dissolved in the aqueous phase, while slow addition of ascorbic acid reduces deactivator Cu(II)-Br<sub>2</sub>/TPMA to activator Cu(I)-Br/TPMA. Oligomeric PMMA is produced in the aqueous phase and later absorbed into the micelle, while the ATRP activator, Cu(I)-Br/TPMA, is transported into the micelle by the phase transfer agent where polymerization occurs (Scheme 1). Polymerizations using TBAB were more controlled and demonstrated low dispersity (&lt;1.17), where those using TBAC displayed higher dispersity (&gt;1.50). First-order linear kinetics for MMA polymerizations at 100 mM TBAB was demonstrated, while reactions deviated from linearity at higher concentrations of TBAB and all concentrations of TBAC.

Mini monomer encapsulated emulsion polymerization of PMMA using ARGET ATRP

256th National Meeting (2018)

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