Bulk nitroxide-mediated polymerization (NMP) of bmyrcene (My)/glycidyl methacrylate (GMA) mixtures with varying GMA molar feed fraction (f GMA,0 5 0.10-0.91) was accomplished at 120 8C, initiated by SG1-based alkoxyamine bearing a N-succinimidyl ester group (NHS-BlocBuilder). Low dispersity My/GMA copolymers ( -D < 1.56) with slight number-average molecular weights (M n s) deviations from predicted values (M n,theo with M n /M n,theo > 70%) were obtained. The copolymerization was revealed to be statistical, confirmed via Fineman-Ross (r My 5 0.80 6 0.31 and r GMA 5 0.71 6 0.15) and Kelen-T€ ud€ os (r My 5 0.48 6 0.12 and r GMA 5 0.53 6 0.18) approaches. Glass transition temperature (T g ) of the statistical P(My-stat-GMA)s increased from 277 to 143 8C as the GMA molar fraction incorporated (F GMA ) increased from 0.10 to 0.90. High SG1 chain-end fidelity for My-rich and GMA-rich P(My-stat-GMA)s was assessed by phosphorus nuclear magnetic resonance ( 31 P NMR, SG1 fraction >69 mol %) and chain-extensions in toluene with My, GMA and styrene (S) (monomodal shift in M n ). Last, diblock P(My-b-GMA) was made and treated with morpholine to produce amphiphilic copolymer able to self-organize into micelles.
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