Atom Transfer Radical Dispersion Polymerization of Styrene in the Presence of PEO‐based Macromonomer

Abstract

Commercially available poly(ethylene oxide) macromonomers are successfully used as reactive stabilizers for atom transfer radical dispersion/precipitation polymerization of styrene. Polystyrene particles with PEO chains covalently anchored on the surfaces are obtained. Control over both the particle size and polymer chain growth is achieved using a two‐stage technique consisting of an initial free radical polymerization (FRP) for the nucleation followed by a reverse atom transfer radical polymerization (ATRP) for the controlled polymerization process. The limited monomer conversion at the FRP step ensures that the overall polymerization process is mainly controlled by the reverse ATRP step, resulting in the formation of particles containing well‐defined polymer chains. magnified image

Polymerization-induced self-assembly driving chiral nanostructured materials

“…[17][18][19][20][21][22][23][24][25][26][27][28] PISA facilitates the formation of a myriad of macromolecular nano-architectures depending on the solvophilic/solvophobic volume ratio at much higher concentrations (up to 50 wt%) by using living radical polymerization techniques, such as atom transfer radical polymerization (ATRP), 29,30 nitroxide mediated polymerization (NMP) [31][32][33] and reversible addition-fragmentation chain transfer (RAFT) polymerization. [17][18][19][20][21][22][23][24][25][26][27][28] PISA facilitates the formation of a myriad of macromolecular nano-architectures depending on the solvophilic/solvophobic volume ratio at much higher concentrations (up to 50 wt%) by using living radical polymerization techniques, such as atom transfer radical polymerization (ATRP), 29,30 nitroxide mediated polymerization (NMP) [31][32][33] and reversible addition-fragmentation chain transfer (RAFT) polymerization.…”

“…During the last six years there has been a prolific interest in polymerization-induced self-assembly (PISA) as a convenient way of making the desired block copolymer morphology which does not need any post-polymerization processing steps. [17][18][19][20][21][22][23][24][25][26][27][28] PISA facilitates the formation of a myriad of macromolecular nano-architectures depending on the solvophilic/solvophobic volume ratio at much higher concentrations (up to 50 wt%) by using living radical polymerization techniques, such as atom transfer radical polymerization (ATRP), 29,30 nitroxide mediated polymerization (NMP) [31][32][33] and reversible addition-fragmentation chain transfer (RAFT) polymerization. 17,20 The contri-butions from Pan, 17 Armes 34 and their co-workers to RAFT dispersion polymerization (RAFTDP) are significant.…”

Better RAFT Control is Better? Insights into the Preparation of Monodisperse Surface-Functional Polymeric Microspheres by Photoinitiated RAFT Dispersion Polymerization

“…Another route to prepare surface-functional polymeric microspheres is the utilization of stabilizers containing functional groups in dispersion polymerization. These functional stabilizers can be macroinitiators, macromonomers, − block copolymers, , or macromolecular chain transfer agents (macro-CTAs). ,− For example, Mckee et al prepared thermoresponsive poly­( N -isopropylacrylamide) (PNIPAM) macromonomers by RAFT polymerization followed by aminolysis and subsequent Michael addition. The obtained PNIPAM macromonomers and macro-CTAs were then used as stabilizers in alcoholic dispersion polymerization.…”

Surface functionalized nano‐objects from oleic acid‐derived stabilizer via non‐polar RAFT dispersion polymerization

“…During last 6 years, considerable efforts have been paid in polymerization‐induced self‐assembly (PISA) via reversible‐deactivation radical polymerization (RDRP) techniques, which has been widely recognized as a convenient and efficient way for the in situ synthesis of block copolymer nano‐objects without performing any post‐polymerization processing steps at relatively high copolymer concentrations (up to 50 wt %) . RDRP methods including atom transfer radical polymerization, nitroxide‐mediated polymerization, reversible addition‐fragmentation chain transfer polymerization (RAFT), organotellurium‐mediated radical polymerization (TERP), and cobalt‐mediated radical polymerization have been readily implemented either in emulsion or dispersion condition. Among the several polymerization techniques, RAFT‐mediated PISA formulation is the most versatile one, which can be conducted with numerous functional monomers in a wide range of solvents, including water, organic polar solvents (lower alcohols such as methanol and ethanol), non‐polar solvents [such as n ‐alkanes, mineral oil, and poly( α ‐olefins)], and also more exotic media such as super critical carbon dioxide and ionic liquids .…”