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.

/pdf/living-radical-polymerization-by-the-raft-process-a-second-3rre2ur7xt.pdf

Living Radical Polymerization by the RAFT Process - A Second Update

Fouling release coatings: a nontoxic alternative to biocidal antifouling coatings.

A living radical polymerization (LRP) is a free radical polymerization that aims at displaying living character, (i.e., does not terminate or transfer and is able to continue polymerization once the initial feed is exhausted by addition of more monomer). However, termination reactions are inherent to a radical process, and modern LRP techniques seek to minimize such reactions, therefore providing control over the molecular weight and the molecular weight distribution of a polymeric material. In addition, the better LRP techniques incorporate many of the desirable features of traditional free radical polymerization, such as compatibility with a wide range of monomers, tolerance of many functionalities, and facile reaction conditions. The control of molecular weight and molecular weight distribution has enabled access to complex architectures and site specific functionality that were previously impossible to achieve via traditional free radical polymerizations. These LRPs are classified in three different subgroups: (1) stable free-radical polymerization such as nitroxide mediated polymerization (NMP),1,2 (2) degenerative transfer polymerization, such as iodine transfer polymerization (ITP and RITP),3,4 single electron transfer-degenerative transfer living radical polymerization(SET-DTLRP),5,6reversibleaddition-fragmentation chain transfer (RAFT),7,8 and macromolecular design via the interchange of xanthates (MADIX)9,10 polymerization, and (3) metal mediated catalyzed polymerization, such as atom transfer radical polymerization (ATRP),11-14 single electron transfer-living radical polymerization (SET-LRP),15 and organotellurium mediated living radical polymrization16-19 Among the existing LRP techniques, RAFT and MADIX are probably the most versatile processes, as they are tolerant * E-mail: T.P.D., T.Davis@UNSW.edu.au; S.P., S.Perrier@ chem.usyd.edu.au. † Centre for Advanced Macromolecular Design (CAMD), School of Chemical Sciences & Engineering, UNSW. ‡ Centre for Advanced Macromolecular Design (CAMD), School of Biotechnology & Biomolecular Sciences, UNSW. § The University of Sydney. Chem. Rev. 2009, 109, 5402–5436 5402

Bioapplications of RAFT polymerization.

Complex polymer architectures via RAFT polymerization: From fundamental process to extending the scope using click chemistry and nature's building blocks

Telechelic polymers by living and controlled/living polymerization methods

The synthesis and characterization of poly(4-hydroxystyrene) (PHS) and poly(4-vinylphenol) (PVPh) by the polymer modification route are reported. Polystyrene prepared by free-radical and anionic polymerization was acetylated quantitatively to poly(4-acetylstyrene) (ACPS) with acetyl chloride and anhydrous aluminum trichloride in carbon disulfide. The acetylation worked equally well in a mixture of 1,2-dichloroethane (DCE) and nitrobenzene containing largely DCE. The extent of the acetylation was estimated by 1 H NMR. The oxidation of ACPS was carried out with various oxidizing agents and reaction conditions. The peracetic acid oxidation in chloroform resulted in quantitative oxidation to poly(4-acetoxystyrene) (APS) as estimated by 1 H NMR spectroscopy. The treatment of APS with hydrazine hydrate in dioxane resulted in the formation of PVPh. Deacetylation occurred with equal versatility in a mixture of aqueous sodium hydroxide and tetrahydrofuran. All the polymers were characterized via gel permeation chromatography, IR, UV, 1 H NMR, and 13 C NMR spectroscopic techniques. This is the first report on the synthesis of ACPS, APS, and PHS of reasonably narrow molecular weight distributions or otherwise by the polymer modification route.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/%28SICI%291099-0518%2820000201%2938%3A3%3C453%3A%3AAID-POLA9%3E3.0.CO%3B2-6

A practical route for the preparation of poly(4-hydroxystyrene), a useful photoresist material

Novel reversible addition−fragmentation chain transfer (RAFT) agents with epoxy- and oxetane-functional groups have been synthesized. Two different methods were used to synthesize the epoxy-functional RAFT agent. An acid-functional chain transfer agent was reacted with either epichlorohydrin (EPI) or glycidol to obtain the epoxy-functional RAFT agent. The epoxy-functional RAFT agent synthesized using EPI had a higher yield. Similarly, the oxetane-functional RAFT agent was obtained by reacting a monofunctional reactive oxetane (3-ethyl-3-hydroxymethyl oxetane) (EHMO) with the acid-functional RAFT agent. The presence of epoxy and oxetane groups on the RAFT agent was confirmed using 1H and 13C nuclear magnetic resonance techniques. Several acrylate monomers and styrene were polymerized using the novel RAFT agents, and in each case the polydispersity was below 1.1. Poly(butyl acrylate) (PBA) synthesized using the epoxy-functional RAFT agent was reacted with acrylic acid to obtain an acrylate-functional PBA. T...

Synthesis and Characterization of Novel Epoxy- and Oxetane-Functional Reversible Addition-Fragmentation Chain Transfer Agents

It is demonstrated that tetrahydrofuran (THF) should be used with caution as a solvent in polymer sample preparation for matrix-assisted laser desorption/ionization (MALDI) analyses. The presence of peroxides in THF may cause the oxidation of chemically active groups. This effect is illustrated in the case of S-containing polystyrene derivatives. The oxidation of the trithiocarbonate group resulted in the formation of poly(styrene)sulfonic acids, R(CH 2 CHPh) n SO 3 H, which was detected in negative mode by MALDI and electrospray ionization (ESI) methods after the samples remained in THF for several hours.

https://www.benicewiczgroup.com/UserFiles/benigroup/Documents/BB44.pdf

The effect of tetrahydrofuran as solvent on matrix-assisted laser desorption/ionization and electrospray ionization mass spectra of functional polystyrenes.

A zwitterionic/amphiphilic pentablock copolymer was prepared using atom transfer radical polymerization (ATRP). The pentablock copolymer is prepared for the atom transfer radical polymerization of a PDMS-PEO-Br macroinitiator and SBMA. The pentablock copolymer is incorporated into a polyurethane coating composition which is useful for antifouling and/or fouling release applications.

Zwitterionic/amphiphilic pentablock copolymers and coatings therefrom

Block copolymer synthesis via a combination of ATRP and RAFT using click chemistry is reported for the first time. A RAFT agent with a terminal propargyl group (PTTC) was synthesized and was used to polymerize butyl acrylate and gave quantitative monomer conversion. Azide-terminated p(tbA) was obtained by ATRP followed by reaction with sodium azide. Later, using CuBr-PMDETA as catalyst via click chemistry, p(tBA)(ATRP) and p(BA)(RAFT) were reacted to get a block copolymer of p(tBA)(ATRP)-b-p(BA)(RAFT). Further, a total of 24 block copolymers were made by reacting four azido functional polymers with six propargyl functional polymers to obtain block copolymers via click chemistry.

Mohammed J. Nasrullah

Papers

A practical route for the preparation of poly(4-hydroxystyrene), a useful photoresist material

Synthesis and Characterization of Novel Epoxy- and Oxetane-Functional Reversible Addition-Fragmentation Chain Transfer Agents

The effect of tetrahydrofuran as solvent on matrix-assisted laser desorption/ionization and electrospray ionization mass spectra of functional polystyrenes.

Zwitterionic/amphiphilic pentablock copolymers and coatings therefrom

Block Copolymer Synthesis via a Combination of ATRP and RAFT Using Click Chemistry