Synthesis of -myrcene/glycidyl methacrylate statistical and amphiphilic diblock copolymers by SG1 nitroxide-mediated controlled radical polymerization

Bulk nitroxide-mediated polymerization (NMP) of -myrcene (My)/glycidyl methacrylate (GMA) mixtures with varying GMA molar feed fraction (f(GMA,0)=0.10-0.91) was accomplished at 120 degrees C, 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,M-theo with M-n/M-n,M-theo>70%) were obtained. The copolymerization was revealed to be statistical, confirmed via Fineman-Ross (r(My)=0.80 +/- 0.31 and r(GMA)=0.71 +/- 0.15) and Kelen-Tudos (r(My)=0.48 +/- 0.12 and r(GMA)=0.53 +/- 0.18) approaches. Glass transition temperature (T-g) of the statistical P(My-stat-GMA)s increased from -77 to +43 degrees C 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 (P-31 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. (c) 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 860-878