Optimization of the nitroxide‐mediated radical polymerization conditions for styrene and tert‐butyl acrylate in an automated parallel synthesizer

Automated parallel synthesizers provide fast and comparable screening of different polymerization parameters under similar conditions. In addition, these robotic systems eliminate handling errors, which may affect the results of a kinetic experiment more than the effect of an important parameter. The polymerization temperature and N,N ‐ tert ‐butyl‐ N ‐[1′‐diethylphosphono‐2,2′‐dimethylpropyl]nitroxide concentration were optimized for the homopolymerization of both styrene and tert ‐butyl acrylate to improve the control over the polymerization while reasonable polymerization rates were retained. Subsequently, polystyrene and poly( tert ‐butyl acrylate) macro initiators were synthesized according to the knowledge obtained from the screening results. These macroinitiators were used for the preparation of block copolymers consisting of styrene and tert ‐butyl acrylate.