Group-transfer polymerization of benzyl methacrylate: A convenient method for synthesis of near-monodisperse poly(methacrylic acid)s

Amphiphilic Block Copolymers in Structure-Controlled Nanomaterial Hybrids

“…An interesting polymer prepared by GTP is poly(2-(dimethylamino)ethylmethacrylate), a polymer that is directly soluble in water. In combination with hydrophobic methacrylate polymers Billingham and coworkers [29,30] synthesized poly((dimethylamino)ethylmethacrylate-bmethacrylate) [31] and poly(2-(dimethylamino) ethylmethacrylate-b-n-butylmethacrylate) [32] or other methacrylates. [33] Micellization in aqueous media as well as the use as stabilizers for the dispersion polymerization of styrene in alcoholic media [34] has been investigated.…”

Nitroxide mediated polymerization of sustainably sourced isobornyl methacrylate and tridecyl methacrylate with acrylonitrile co‐monomer

“…Until recently, anionic, cationic, and group transfer polymerizations were the only “living” techniques available that efficiently controlled the structure and architecture of polymers. Although these methods ensure low dispersity materials with controlled molecular weight and defined chain ends, they are not useful for the polymerization and copolymerization of a wide range of functionalized monomers owing to the incompatibility of the growing polymer chain end (anion or cation) with numerous functional groups and certain monomer families . Furthermore, such polymerization methods require stringent reaction conditions including the use of ultrapure reagents and the total exclusion of moisture and oxygen.…”

“…Although these methods ensure low dispersity materials with controlled molecular weight and defined chain ends, they are not useful for the polymerization and copolymerization of a wide range of functionalized monomers owing to the incompatibility of the growing polymer chain end (anion or cation) with numerous functional groups and certain monomer families. [1][2][3][4][5] Furthermore, such polymerization methods require stringent reaction conditions including the use of ultrapure reagents and the total exclusion of moisture and oxygen. Over the past two decades, controlled radical polymerization (CRP) provided a new synthetic tool to easily achieve complex macromolecular architectures with narrow molecular weight distribution and controlled microstructure, without the strict requirements to obtain such polymers by classical "living" polymerizations.…”

First example of the atom transfer radical polymerisation of an acidic monomer: direct synthesis of methacrylic acid copolymers in aqueous media

“…5 Near-monodisperse acidic copolymers can be readily prepared via anionic (group transfer) polymerisation using either tert-butyl or benzyl methacrylate as a protected monomer for methacrylic acid. 6,7 In principle ATRP can also be used for such protected monomer syntheses, but in practice Haddleton and coworkers have reported very slow polymerisation for sterically hindered monomers such as tert-butyl methacrylate. 8 Moreover, in a recent review article, Patten and Matyjaszewski state that 'acrylic and methacrylic acid cannot be polymerised with currently available ATRP catalysts, because these monomers react rapidly with the metal complexes to form metal carboxylates that are inefficient deactivators and cannot be reduced to active ATRP catalysts'.…”