Photoinitiated copper-mediated radical polymerization offers an one-pot and time efficient method of preparing a decablock copolymer PMA-PtBA-PMA-PDEGA-PMA-PtBA-PMA-PDEGA-PnBA-PDEGA with an overall molecular weight of 8500 g·mol–1. The molecular weight is in close agreement with theoretical expectations and significantly narrow dispersities (Đ = 1.1–1.17) are achieved for the various block extensions. The tert-butyl group of the decadeblock was deprotected to form PMA-PAA-PMA-PDEGA-PMA-PAA-PMA-PDEGA-PnBA-PDEGA. The deprotection is confirmed by the disappearance of tert-butyl signal and the loss of molecular weight investigated by 1H NMR and SEC, respectively. The carboxylic group of PAA is protonated in acidic solution (water insoluble) and deprotonated in basic solution (water-soluble). This enables a conformational change of PMA-PAA-PMA-PDEGA-PMA-PAA-PMA-PDEGA-PnBA-PDEGA in water/ethanol mixture (80/20%v/v), as is demonstrated by a turbid solution at pH 2 and transparent solutions at pH 10.

The use of photo-induced copper-mediated radical polymerization ( photoCMP) to synthesize mixed acrylate/methacrylate (methyl acrylate, MA and methyl methacrylate, MMA) block copolymers is investigated. Reactions in which only one type of ligand (Me 6 TREN) is used lead to unsuccessful outcomes of polymerization due to a mismatch in reactivity of the two monomers. A ligand exchange to PMDETA for methacrylate is required to obtain good block structures. Due to insufficient re-initiation of polyacrylates, methyl methacrylate needs to be polymerized first, before acrylate can be added for chain extension. A halogen exchange with CuCl is found to be beneficial to increase the re-initiation behaviour of the polyacrylate with respect to the acrylate chain propagation, but inherently compromises the livingness of the polymerization. Successful synthesis of block copolymers is only observed when the PMMA block is polymerized first and if all PMDETA ligand and residual monomer are removed prior to acrylate chain extension. The batch-type photoreactions are then transferred to a continuous flow tubular photoreactor, which leads to a significant acceleration of polymerizations, concomitant reduction in product dispersity and largely simplified block copolymer synthesis conditions. † Electronic supplementary information (ESI) available. See