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Efficient transfer of halogen atoms is essential for controlling the growth of polymers in atom transfer radical polymerization (ATRP). The nature of halogens may influence the efficiency of the halogen atom transfer during the activation and deactivation processes. The effect of halogens can be associated with the C–X bond dissociation energy and the affinity of the halogens/halides to the transition metal catalyst. In this paper, we study the effect of halogens (Br vs. Cl) and reaction media in iron-catalyzed ATRP in the presence of halide anions as ligands. In Br-based initiating systems, polymerization of methacrylate monomers was well-controlled whereas Cl-based initiating systems provided limited control over the polymerization. The high affinity of the Cl atom to the iron catalyst renders it less efficient for fast deactivation of growing chains, resulting in polymers with molecular weights higher than predetermined by Δ[M]/[RX] o and with high dispersities. Conversely, Br can be exchanged with higher efficiency and hence provided good control over polymerization. Decreasing the polarity of the reaction medium improved the polymerization control. Polymerizations using ppm levels of the iron catalyst in acetonitrile (a more polar solvent) yielded polymers with larger dispersity values due to the slow rate of deactivation as opposed to the less polar solvent anisole, which afforded well-controlled polymers with dispersity <1.2. 

Despite their industrial ubiquity, polyolefin‐polyacrylate block copolymers are challenging to synthesize due to the distinct polymerization pathways necessary for respective blocks. This study utilizes MILRad, metal–organic insertion light‐initiated radical polymerization, to synthesize polyolefin‐b‐poly(methyl acrylate) copolymer by combining palladium‐catalyzed insertion–coordination polymerization and atom transfer radical polymerization (ATRP). Brookhart‐type Pd complexes used for the living polymerization of olefins are homolytically cleaved by blue‐light irradiation, generating polyolefin‐based macroradicals, which are trapped with functional nitroxide derivatives forming ATRP macroinitiators. ATRP in the presence of Cu(0), that is, supplemental activators and reducing agents , is used to polymerize methyl acrylate. An increase in the functionalization efficiency of up to 71% is demonstrated in this study by modifying the light source and optimizing the radical trapping condition. Regardless of the radical trapping efficiency, essentially quantitative chain extension of polyolefin‐Br macroinitiator with acrylates is consistently demonstrated, indicating successful second block formation.