Macromolecular design via reversible addition–fragmentation chain transfer (RAFT)/xanthates (MADIX) polymerization

Abstract

Among the living radical polymerization techniques, reversible addition-fragmentation chain transfer (RAFT) and macromolecular design via the interchange of xanthates (MADIX) polymerizations appear to be the most versatile processes in terms of the reaction conditions, the variety of monomers for which polymerization can be controlled, tolerance to functionalities, and the range of polymeric architectures that can be produced. This review highlights the progress made in RAFT/MADIX polymerization since the first report in 1998. It addresses, in turn, the mechanism and kinetics of the process, examines the various components of the system, including the synthesis paths of the thiocarbonyl-thio compounds used as chain-transfer agents, and the conditions of polymerization, and gives an account of the wide range of monomers that have been successfully polymerized to date, as well as the various polymeric architectures that have been produced. In the last section, this review describes the future challenges that the process will face and shows its opening to a wider scientific community as a synthetic tool for the production of functional macromolecules and materials.

Synthesis of Amphiphilic Tadpole-Shaped Linear-Cyclic Diblock Copolymers via Ring-Opening Polymerization Directly Initiating from Cyclic Precursors and Their Application as Drug Nanocarriers

“…[1][2][3] It has been well-established that the topological structures and chemical composition of nonlinearshaped block copolymers can exhibit dramatic effects on the solution properties and self-assembling morphologies as compared with their linear counterpart. [4][5][6][7][8][9] It is worthy of noting that the developments of a variety of controlled radical polymerization techniques 10 such as atom transfer radical polymerization (ATRP), [11][12][13] reversible addition-fragmentation chain transfer (RAFT) polymerization, [14][15][16] and nitroxide-mediated polymerization (NMP) 17,18 have facilitated the synthesis of nonlinear-shaped polymers with varying chain architectures such as cyclic, 8,9,[19][20][21][22][23] (miktoarm) star, [24][25][26] star block copolymers, 27,28 comb, [29][30][31][32] sun-shaped, [33][34][35] H-shaped, [36][37][38] and θ-shaped 39,40 polymers. Among these nonlinear chain topologies, tadpole-shaped linearcyclic diblock copolymers [41]…”

In situ bidentate to tetradentate ligand exchange reaction in cobalt-mediated radical polymerization

“…In the case of vinyl esters and some vinyl amides, DFT modeling showed that an extra-stabilization of the CACo bond occurred via an intramolecular chelation of the cobalt atom with the carbonyl function of the last monomer unit and is responsible for the good control observed (Scheme 2) [51,64]. This intramolecular chelation is made possible by the flexible geometry of Co(acac) 2 [67,68] that is not possible for cobalt complexes bearing tetradentate ligands with a rigid square-pyramidal geometry (such as cobalt porphyrins) [55,69,70]. Co(acac) 2 is however less efficient for acrylates polymerization as the result of the low stability of the CACo bond of the dormant species [71].…”

“…Controlled radical polymerization CRP has become an important tool for the preparation of well-defined polymer materials [1][2][3][4][5][6][7][8][9]. The use of organometallic complexes was a significant step towards the development of CRP of various vinylic monomers [1,[9][10][11][12].…”

“…Salen type ligands, in a one-pot process (Scheme 3, route C) for improving the block copolymerization of vinyl acetate and n-butyl acrylate (Scheme 4). Prior to investigate the block copolymerizations, the performances of Co(Salen) for VAc and nBA polymerizations are explored and compared to those of Co(acac) 2 and Co(Salen*).…”

Fluorescently Labeled Protein-Polymer Bioconjugates Using Protein-Derived Macroinitiators from Living Radical Polymerization

“…Transition-metal-mediated living radical polymerization (also called atom transfer radical polymerization, A TRP) ( 6, 7), nitroxide-mediated polymerization (NMRP) (8) and reversible transfer as reversible addition fragmentation transfer (RAFT) (9) allow various tailor-made polymers featuring unique properties in terms of molecular weight, molar mass distribution and chi;tin-end functionality to be synthesized. This provides a powerful tool for protein/peptide biology.…”