Low-Dispersity Polymers in Ab Initio Emulsion Polymerization: Improved MacroRAFT Agent Performance in Heterogeneous Media

Abstract

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Influence of structure and solubility of chain transfer agents on the RAFT control of dispersion polymerisation in scCO2

“…This results in a low MMA/DDMAT molar ratio in the dispersed phase, which can overcome the low chain transfer constant of DDMAT, in a similar fashion as described by Perrier and co-workers. 57 In this way we can rationalise the surprisingly good control observed with DDMAT.…”

“…Good polymerisation control with a poorly selected CTA has been very recently demonstrated in RAFT emulsion polymerisation. 57 Such result, is only possible if a low MMA/CTA molar ratio is effectively established inside the particles throughout the reaction. In our system, as MMA is mainly consumed inside the particles, the monomer is continuously supplied to maintain an overall constant concentration of MMA within the particles (with respect to PMMA and CO 2 ), establishing a limiting feed, until there is no more MMA in the continuous phase.…”

Synthesis of Multicompositional Onion‐like Nanoparticles via RAFT Emulsion Polymerization

“…[3] Theuse of RDRP techniques for one-pot synthesis of multiblock copolymers has received great interest. [2,4] Pioneering work on multiblock copolymer synthesis in one-pot was reported in 2011 using Cu 0 -mediated radical polymerization, [2b] demonstrating that RDRP under conditions that support high livingness and chain end fidelity can be employed for synthesis of high-order multiblock copolymers.…”

How the Reactive End Group of Macro‐RAFT Agent Affects RAFT‐Mediated Emulsion Polymerization‐Induced Self‐Assembly

“…Owing to the intrinsic mechanism of RAFT-mediated emulsion polymerization that monomer needs to diffuse from monomer droplets to micelles, the problem of monomer order of multiblock copolymers and RAFT controllability in RAFT polymerization can be largely overcome. [49][50][51] Moreover, a diverse set of morphologies including spheres, worms, and vesicles can also be obtained by changing reaction conditions in RAFT-mediated emulsion polymerization such as monomer type, reaction temperature, polymer architecture, and degree of polymerization (DP). [52][53][54][55][56][57][58][59][60][61][62] Although great progress has been made in RAFT-mediated emulsion polymerization, almost all RAFT-mediated emulsion polymerizations are limited to the preparation of AB diblock copolymer nano-objects using monofunctional macro-RAFT agents with non-reactive end groups.…”