Molecular Weight Distribution Of Two Types Of Living Chains Formed During Nitroxide-Mediated Polymerization Of Styrene

Different types of polymer chains generated during the nitroxide-mediated polymerization of styrene are separated for the first time, and their molecular weight distribution (MWD) is investigated. Living and dead chains are monitored during the reaction; specifically, two types of living chains derived from the initiation of the alkoxyamine (R-T) and the self-initiation of styrene and dead chains present in the as-prepared polystyrene (PS). To distinguish between each polymer species, different numbers of hydroxyl groups are introduced onto the T and R groups of the alkoxyamine (one and two groups, respectively). Each living and dead chains is resolved according to the distinct number of hydroxyl groups on its chain-end using high-performance liquid chromatography. Molecular structures of the fractionated PS are characterized using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and H-1 nuclear magnetic resonance spectroscopy, and the results of which show two distinct initiation paths: one originating from R-T and the other from the self-initiation of styrene. Molecular weight and MWD are measured using size-exclusion chromatography and reveal a narrow MWD for the living chains derived from R-T. Contrastingly, a broad and skewed MWD is observed for the other living chains derived from the self-initiation of styrene and the dead chains.