Graft polymer synthesis by RAFT transfer‐to

Abstract

The synthesis of graft polymers via controlled polymerization techniques has enabled the facile modification of the surface properties of a variety of substrates. Three grafting methods are typically highlighted in the literature: grafting‐to, grafting‐from, and grafting‐through. However, a fourth method exists when grafting is conducted using reversible addition‐fragmentation chain transfer (RAFT) polymerization, which we refer to as transfer‐to. Transfer‐to differs from the other grafting strategies in the types of structural defects and impurities that arise during polymerization. This review addresses important considerations when conducting RAFT transfer‐to, including RAFT chain transfer agent selection, monomer structure, and reaction conditions. In addition, we highlight key mechanistic differences between grafting‐from and transfer‐to and their effects on the structure and sample composition of the resulting graft polymers. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 2865–2876

Polymerizations by RAFT: Developments of the Technique and Its Application in the Synthesis of Tailored (Co)polymers

“…Polymers prepared by RAFT have been used in many different fields, notably in preparation of biomaterials (implants, scaffolds, coatings, drug, gene delivery, etc. ), [ 226–230 ] sensing and detection, [ 231,232 ] coatings and patterning, [ 233–235 ] electronics, [236] nanocomposite, [ 235,237–240 ] and vitrimers. [ 241 ] One of the most recent and emerging applications of polymers and nanoparticles prepared by RAFT is membranes for separation.…”

Synthetic Methodologies for Chelating Polymer Ligands: Recent Advances and Future Development

“…RAFT polymerization allows to obtain CPLs, for example poly(vinyl esters) by elongating the chain of macroRAFT‐agents containing chelating fragments . In addition, RAFT grafting (Figure ) differs from the other grafting approaches in the types of structural defects and impurities that arise during polymerization …”

“…[62] In addition, RAFT grafting ( Figure 2) differs from the other grafting approaches in the types of structural defects and impurities that arise during polymerization. [63] Scheme 9. Synthesis of chelating PP-g-PIDA materials via a 2-step laminated photo-grafting process.…”

Cationic Bottlebrush Polymers from Quaternary Ammonium Macromonomers by Grafting‐Through Ring‐Opening Metathesis Polymerization

“…The grafting‐from approach, which polymerizes side chains from a backbone initiator, can form bottlebrushes with long backbones, but can lead to side chain defects due to the increased likelihood of radical–radical coupling in some syntheses 24–26. The transfer‐to technique is similar to the grafting‐from approach except the chain transfer agent remains on the polymer backbone and active radicals exist on free polymer chains, which can eliminate side reactions present in the grafting‐from method, however; termination defects still exist during polymerization 27,28. To prepare a completely dense bottlebrush polymer, the grafting‐through method is commonly used by polymerizing macromonomers (MMs) with a reactive end group 18,29,30…”