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Reversible-deactivation radical polymerization (RDRP) serves as a powerful tool nowadays for the preparations of unique linear and non-linear macromolecules. In this study, enhanced spin capturing polymerizations (ESCPs) of styrene (St) and tert -butyl acrylate (tBA) monomers were, respectively, conducted in the presence of difunctional (1Z,1'Z)-1,1'-(1,4-phenylene) bis ( N - tert -butylmethanimine oxide) (PBBN) nitrone. Four-arm (PSt) 4 and (PtBA) 4 star macroinitiators (MIs) can be afforded. By correspondingly switching the second monomer (i.e., tBA and St), miktoarm star copolymers (μ-stars) of (PSt) 2 -μ-(PtBA- b -PSt) 2 and (PtBA) 2 -μ-(PSt- b -PtBA) 2 ) were thus obtained. We further conducted hydrolysis of the PtBA segments to PAA (i.e., poly(acrylic acid)) in μ-stars to afford amphiphilic μ-stars of (PSt) 2 -μ-(PAA- b -PSt) 2 and (PAA) 2 -μ-(PSt- b -PAA) 2 . We investigated each polymerization step and characterized the obtained two sets of "sequence-isomeric" μ-stars by FT-IR, 1 H NMR, differential scanning calorimeter (DSC), and thermogravimetric analysis (TGA). Interestingly, we identified their physical property differences in the case of amphiphilic μ-stars by water contact angle (WCA) and atomic force microscopy (AFM) measurements. We thus proposed two microstructures caused by the difference of polymer chain sequences. Through this polymerization transformation ( Ŧ ) approach (i.e., ESCP- Ŧ -NMP), we demonstrated an interesting and facile strategy for the preparations of μ-stars with adjustable/switchable interior and exterior polymer structures toward the preparations of various nanomaterials.

nanomaterials

Miktoarm Star Copolymers Prepared by Transformation from Enhanced Spin Capturing Polymerization to Nitroxide-Mediated Polymerization (ESCP-Ŧ-NMP) toward Nanomaterials