Block copolymer synthesis in one shot: concurrent metal-free ATRP and ROP processes under sunlightElectronic supplementary information (ESI) available: Experimental data, 1H-NMR spectra and GPC traces of the block copolymers. See DOI: 10.1039/c7py00069cThis manuscript is dedicated to Wolfram Schnabel, who passed away on February 1, 2017. He made a great deal of contribution to polymer photochemistry

A completely metal-free strategy was developed by combining Atom Transfer Radical Polymerization (ATRP) and Ring Opening Polymerization (ROP) for the syntheses of block copolymers. These two different metal-free controlled/living polymerizations, which have no effect on each other, were concurrently realized in one reaction medium. Using a specifically designed bi-functional initiator, possessing primary hydroxyl and tertiary bromide functionalities, vinyl and lactone monomers were simultaneously polymerized under sunlight, by metal-free strategies. Spectral and chromatographic results reveal that the synthetic approach applied produces block copolymers in a controlled manner, free from homopolymers, and with narrow molecular weight distributions. A completely metal-free strategy was developed by combining Atom Transfer Radical Polymerization (ATRP) and Ring Opening Polymerization (ROP) for the syntheses of block copolymers.