Recent achievements in anionic polymerization of (meth)acrylates

Nitroxide‐Mediated Polymerization of Methyl Methacrylate Using an SG1‐Based Alkoxyamine: How the Penultimate Effect Could Lead to Uncontrolled and Unliving Polymerization

“…Up to now, this kind of block copolymers have been prepared by anionic polymerization, especially ligated anionic polymerization [7] (LAP). For two decades, living polymerizations have been achieved through a more Summary: The nitroxide-mediated polymerization (NMP) of MMA initiated with a new crowded SG1-based alkoxyamine was performed.…”

Physical Properties of PBMA‐b‐PBA‐b‐PBMA Triblock Copolymers Synthesized by Atom Transfer Radical Polymerization

“…Block copolymers of (meth)acrylic monomers are not only synthetically challenging [7] but also interesting because of their morphological characteristics and mechanical properties. The variety of these monomers allows the fine tuning of the glass transition temperature and the (im)miscibility of the constitutive blocks of the copolymers.…”

Synthesis of ?- and ?,?-sulfonatotelechelics based on homopolymers and block copolymers ofn-butyl methacrylate andt-butyl methacrylate

“…These difficulties were largely overcome during the past 2 decades by careful selection of reaction conditions, for example, a polar solvent (THF) at a low temperature (Ϫ78°C) and a bulky initiator. [5][6][7] The introduction of a propagating center ligand such as LiCl to the reaction, in particular, led to the truly living anionic polymerization of some methacrylates and even of a few acrylates, allowing the preparation of methacrylate-and acrylate-based block copolymers with a predictable molecular weight and a narrow molecular weight distribution. 5 On the basis of these achievements, the anionic polymerization of nBMA was investigated in THF at Ϫ78°C with either 1,1-diphenyl-3-methylpentyllithium or dilithium 1,1,4,4-tetraphenylbutane as monofunctional or difunctional initiators, respectively, with or without LiCl.…”

“…The living anionic polymerization of acrylate and methacrylate monomers is a relatively recent achievement. 5 The anionic polymerization of these monomers suffers from side reactions due to the sensitivity of carbonyl groups on the side chain and the ␣-hydrogen atom (in the acrylates) toward nucleophilic attack, giving rise to chain transfer and deactivation processes. The side reactions can be minimized by careful selection of the reaction conditions, typically a polar solvent, a low reaction temperature, a bulky initiator, and a stabilizer for the anionic propagating centers.…”

“…The side reactions can be minimized by careful selection of the reaction conditions, typically a polar solvent, a low reaction temperature, a bulky initiator, and a stabilizer for the anionic propagating centers. [5][6][7] Under these conditions, acrylate-and methacrylate-based block copolymers with a predictable molecular weight and a narrow molecular weight distribution can be obtained. These achievements open the way for the synthesis of novel telechelic polymers based on these monomers.…”