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

Conformational studies by dynamic NMR. Part XV. The rotational barrier of N-methyl aniline☆

Reactivity of glucosyl radical in the presence of phenols

The low-temperature n.m.r. spectra at the 13C frequency (25.16 MHz) showed the non-equivalence of the ortho- and meta-carbons in a number of substituted N-alkylanilines. Line-shape analysis, or measurement at the coalescence temperature, yielded the free energy of activation for the rotational process about the C–N bond. The ΔG‡ values were found to be linearly related to the Hammett constants for a variety of para-substituted derivatives. The barriers were found also to decrease with an increase in the size of the alkyl substituents bonded to the nitrogen atom.

Conformational studies by dynamic nuclear magnetic resonance spectroscopy. Part 19. Substituent effects upon the rotational barrier of alkylanilines

Mesure des barrieres d'interconversion entre les deux conformeres enantiomeres de torsion par spectrometre RMN 1 H et 13 C. On montre que les substituants electrodonneurs et electroattracteurs en position 4 augmentent et diminuent respectivement la barriere d'interconversion des napthyl-1 amines tertiaires

Conformational studies by dynamic NMR. 35. Structure, conformation, and stereodynamics of hindered naphthylamines

Rotational barriers about the N(1)–N(2) bond in a number of 1,1-dialkyl-3-aryltriazenes (R2N·N:NAr) have been measured by line-shape analysis of the n.m.r. signals. It has been observed that the barrier is only slightly affected by the bulkiness of the alkyl groups but is substantially lowered when the triazenes contain the piperidyl ring with two (DMP) or four (TMP) methyl groups in positions 2 and 6. This feature is explained in the DMP derivatives as being due to the repulsion of the two axial cis-methyl groups; this conformation has been confirmed by X-ray diffraction. In TMP derivatives, the lowering of the barrier can be explained by assuming a non-chair (twisted) conformation for the piperidyl ring in solution. 13C N.m.r. spectra also seem to support this conformation.

Dante Macciantelli

Papers

Conformational studies by dynamic NMR. Part XV. The rotational barrier of N-methyl aniline☆

Reactivity of glucosyl radical in the presence of phenols

Conformational studies by dynamic nuclear magnetic resonance spectroscopy. Part 19. Substituent effects upon the rotational barrier of alkylanilines

Conformational studies by dynamic NMR. 35. Structure, conformation, and stereodynamics of hindered naphthylamines

Conformational studies by dynamic nuclear magnetic resonance. Part X. Stereodynamics and conformations of hindered triazenes