Abstract
We demonstrate thorough studies on copolymerization of methyl methacrylate (MMA) with widely used commercially available functional monomers, allyl methacrylate (AMA), 2‐hydroxyethyl methacrylate (HEMA), glycidyl methacrylate (GMA) and N‐isopropyl acrylamide (NIPAM), via Cu(0)‐mediated reversible deactivation radical polymerization (Cu(0)‐RDRP), and further compared to copolymerization kinetics of MMA with ethyl methacrylate (EMA). The apparent propagation rate constants and induction periods of the copolymerizations were estimated to reveal the effect of monomer type to copolymerization kinetics. Further studies show that MMA/AMA and MMA/HEMA exhibit relatively random distributions of functional monomer units in copolymer chains; however, MMA/NIPAM does not as activated MMA and NIPAM prefer homopolymerization and crosspolymerization, respectively. Copolymerization conditions for all pairs show less reactivity differences compared to the cases of other radical‐based polymerizations, highlighting the importance of polymerization methods and conditions to control copolymer microstructure, and emphasizing the significance of deeper understanding in RDRPs.
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