Universal Conditions for the Controlled Polymerization of Acrylates, Methacrylates, and Styrene via Cu(0)-RDRP

Abstract

Usually atom transfer radical polymerization (ATRP) requires various parameters, such as the type of initiator, transition metal, ligand, solvent, temperature, deactivator, added salts and reducing agents, need to be optimised in order to achieve a high degree of control over molecular weight and dispersity. These components play a major role when switching monomers e.g. from acrylic to methacrylic and/or styrenic monomers during the synthesis of homo-and block copolymers as the stability and reactivity of the carbon centered propagating radical dramatically changes. This is a challenge for both "experts" and non-experts as choosing the appropriate conditions for successful polymerization can be time consuming and an arduous task. In this work we describe some universal conditions for the efficacious polymerization of acrylates, methacrylates and styrene (using an identical initiator, ligand, copper salt and solvent) based on commercially available reagents (PMDETA, IPA, Cu(0) wire). The versatility of these conditions is demonstrated by the near quantitative polymerization of these monomer families to yield well-defined materials over a range of molecular weights with low dispersities (~1.1-1.2). The control and high end group fidelity is further exemplified by in situ block copolymerization upon sequential monomer addition for the case of methacrylates and styrene furnishing higher molecular weight copolymers with minimal termination. The facile nature of these conditions, combined with readily available reagents will greatly expand the access and availability of tailored polymeric materials to all researchers.

Graft modification of methyl acrylate onto chicken feather via surface initiated Cu(0)‐mediated reversible‐deactivation radical polymerization

“…Polymerizations were performed and named for feather‐g‐PMA n , where n denotes the target Dp . As expected, homo polymerization of MA initiated by EBIB in DMSO exhibited good control according to low PDI (~1.1) and good correspondence of theoretical molecular mass and GPC measured value the same as those of numerous reports . When adopting PMMA as a calibration standard, the molecular masses measured by GPC were slightly higher than theoreticalvalues because of different monomer molecular masses.…”

“…However, Cu(0)‐mediated RDRP also have limitations in monomer and solvent selection. To be specific, less active monomers and acidic monomers are hard to process …”

Solvent effects on the intramolecular charge transfer character of N,N‐diaryl dihydrophenazine catalysts for organocatalyzed atom transfer radical polymerization

“…These optimizations were successful in realizing closely similar outcomes for 5 different catalysts to produce polymers with low Đ through achieving high I * in the polymerization of MMA. Different ATRP catalysts commonly require selectively tuned experimental conditions to operate a controlled polymerization, and these data represent the advantages and robustness of using N , N ‐diaryl dihydrophenazines capable of accessing CT in their lowest energy excited states, in contrast to the non‐CT derivatives.…”

Activation of alkyl halides at the Cu0 surface in SARA ATRP: An assessment of reaction order and surface mechanisms

“…It has successfully been utilized in the polymerization of acrylates, methacrylates, styrenes, acrylonitrile, and acrylamides with varying macromolecular architectures . This widespread control has been achievable in a broad range of reaction media including both aqueous and organic solvents …”