Abstract
Poly(acrylic acid-ran-styrene) (P(AA-r-S)) and poly(tert-butyl acrylate-ran-styrene) (P(tBuA-r-S)) random copolymers previously made with different molar ratios (0, 4.5, and 9 mol %) of additional free nitroxide mediator, N-tert-butyl-N-[1-(diethylphosphono)-2,2-dimethylpropyl]nitroxide (SG1), relative to 2-[[N-tert-butyl-N-[1-(diethylphosphono)-2,2-dimethylpropyl]amino]oxy]-2-methylpropionic acid (BlocBuilder) alkoxyamine unimolecular initiator were used as macroinitiators for styrene chain extension. The reinitiating experiments were performed in the bulk at 115 °C when using P(tBuA-r-S) macroinitiators or 30−50 wt % dioxane solution at 120 °C when using P(AA-r-S) macroinitiators. The P(tBuA-r-S)-containing macroinitiators (number-average molecular weight Mn = 13.4−25.8 kg·mol−1) with polydispersities Mw/Mn = 1.13−1.57 were capable of initiating chains extended with styrene as indicated by monomodal and narrow molecular weight distributions with Mn = 34.6−66.3 kg·mol−1 and Mw/Mn ranging from 1.24 ...
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