This paper presents a review of living radical polymerization achieved with thiocarbonylthio compounds [ZC(=S)SR] by a mechanism of reversible addition–fragmentation chain transfer (RAFT). Since we first introduced the technique in 1998, the number of papers and patents on the RAFT process has increased exponentially as the technique has proved to be one of the most versatile for the provision of polymers of well defined architecture. The factors influencing the effectiveness of RAFT agents and outcome of RAFT polymerization are detailed. With this insight, guidelines are presented on how to conduct RAFT and choose RAFT agents to achieve particular structures. A survey is provided of the current scope and applications of the RAFT process in the synthesis of well defined homo-, gradient, diblock, triblock, and star polymers, as well as more complex architectures including microgels and polymer brushes.

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Living radical polymerization by the RAFT process

This paper provides a third update to the review of reversible deactivation radical polymerization (RDRP) achieved with thiocarbonylthio compounds (ZC(=S)SR) by a mechanism of reversible addition-fragmentation chain transfer (RAFT) that was published in June 2005 (Aust. J. Chem. 2005, 58, 379). The first update was published in November 2006 (Aust. J. Chem. 2006, 59, 669) and the second in December 2009 (Aust. J. Chem. 2009, 62, 1402). This review cites over 700 publications that appeared during the period mid 2009 to early 2012 covering various aspects of RAFT polymerization which include reagent synthesis and properties, kinetics and mechanism of polymerization, novel polymer syntheses, and a diverse range of applications. This period has witnessed further significant developments, particularly in the areas of novel RAFT agents, techniques for end-group transformation, the production of micro/nanoparticles and modified surfaces, and biopolymer conjugates both for therapeutic and diagnostic applications.

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Living Radical Polymerization by the RAFT Process - A Second Update

Tetrathiafulvalenes, oligoacenenes, and their buckminsterfullerene derivatives: the brick and mortar of organic electronics.

Radical addition-fragmentation chemistry in polymer synthesis

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. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43:5347–5393, 2005

https://www.onlinelibrary.wiley.com/doi/pdf/10.1002/pola.20986

Macromolecular design via réversible addition-fragmentation chain transfer (RAFT)/Xanthates (MADIX) polymerization

Irradiation of a number of different sutures largely employed in the clinical practice with either high energy electrons or with γ-rays followed by quenching with glycidyl methacrylate (GMA) conveniently led to derivatization through a radical-based process. The radicals involved were detected by means of ESR spectroscopy and were characterized on the basis of their ESR spectral parameters which were also found to be consistent with the hfs constants predicted by DFT calculations. Evidence of the GMA derivatization of the sutures was obtained via13C CP-MAS NMR spectroscopy, while its extent was evaluated gravimetrically.

Radical-based grafting of GMA on sutures of different nature.

Evidence of the existence of correlated intramolecular orientation (gear effect) has been observed in Pri2NNO (1) and Pri2NNNPh (2) by 13C nmr In the first case two conformers have been detected in a 92 :8 ratio at –120 °C The corresponding activation parameters have been measured (ΔG‡ 97 kcal mol–1) and the structures of the two conformers assigned Molecular mechanics calculations reproduce all the experimental observations and indicate, in addition, that this dynamic process is not synchronous but follows a two-step pathway In the case of (2) the existence of the phenomenon could be detected through the interpretation of the selective broadening of one spectral line, and the free energy of activation could be measured (ΔG‡ 102 kcal mol–1) even though the spectrum of the less populated conformer was not directly detected

Conformational studies by dynamic nuclear magnetic resonance. Part 24. Gear effect in di-isopropyl-nitrosoamine and -phenyltriazene studied by carbon-13 nuclear magnetic resonance and molecular mechanics

Dante Macciantelli

Papers

Radical-based grafting of GMA on sutures of different nature.

Conformational studies by dynamic nuclear magnetic resonance. Part 24. Gear effect in di-isopropyl-nitrosoamine and -phenyltriazene studied by carbon-13 nuclear magnetic resonance and molecular mechanics

Radiochromic properties of α–terthiophene–cellulose triacetate films

Conformational studies by dynamic NMR—28 : Stereomutations in some di-, tri- and tetraalkylhydrazines

The conformational preferences of isomeric naphthaldehydes as determined by NOE experiments