Living radical polymerization fragmentation chain transfer

Controlled/ Living radical polymerization (CRP) of vinyl acetate (VAc) via nitroxide-mediated polymerization (NMP), organocobalt-mediated polymerization, iodine degenerative transfer polymerization (DT), reversible radical addition-fragmentation chain transfer polymerization (RAFT), and atom transfer radical polymerization (ATRP) is summarized and compared with the ATRP of VAc catalyzed by copper halide/2,2 6 ,2 -terpyridine. The new copper catalyst provides the first example of ATRP of VAc with clear mechanism and the facile synthesis of poly(vinyl acetate) and its block copolymers. 

VAc has been successfully polymerized via controlled/ living radical polymerization techniques including nitroxide-mediated polymerization, organometallic-mediated polymerization, iodine-degenerative transfer polymerization, reversible radical addition-fragmentation chain transfer polymerization, and atom transfer radical polymerization. These methods can be used to prepare well-defined various polymer architectures based on PVAc and poly(vinyl alcohol). The copper halide/t is an active ATRP catalyst for VAc, providing a facile synthesis of PVAc and its block copolymers. Further developments of this catalyst will be the improvements of catalytic efficiency and polymerization control. 

While in most of the reports on SIP free radical polymerization is utihzed, the restricted synthetic possibihties and lack of control of the polymerization in terms of the achievable variation of the polymer brush architecture limited its use. The alternatives for the preparation of weU-defined brush systems were hving ionic polymerizations. Recently, controlled radical polymerization techniques has been developed and almost immediately apphed in SIP to prepare stracturally weU-de-fined brush systems. This includes living radical polymerization using nitroxide species such as 2,2,6,6-tetramethyl-4-piperidin-l-oxyl (TEMPO) [285], reversible addition fragmentation chain transfer (RAFT) polymerization mainly utilizing dithio-carbamates as iniferters (iniferter describes a molecule that functions as an initiator, chain transfer agent and terminator during polymerization) [286], as well as atom transfer radical polymerization (ATRP) were the free radical is formed by a reversible reduction-oxidation process of added metal complexes [287]. All techniques rely on the principle to drastically reduce the number of free radicals by the formation of a dormant species in equilibrium to an active free radical. By this the characteristic side reactions of free radicals are effectively suppressed. 

Chiefari J, Chong YK, Ercole F (1998) Living free radical polymerization by reversible addition-fragmentation chain transfer -the RAFT process. Macromolecules 31 5559-5562... 

Hawker et al. 2001 Hawker and Wooley 2005). Recent developments in living radical polymerization allow the preparation of structurally well-defined block copolymers with low polydispersity. These polymerization methods include atom transfer free radical polymerization (Coessens et al. 2001), nitroxide-mediated polymerization (Hawker et al. 2001), and reversible addition fragmentation chain transfer polymerization (Chiefari et al. 1998). In addition to their ease of use, these approaches are generally more tolerant of various functionalities than anionic polymerization. However, direct polymerization of functional monomers is still problematic because of changes in the polymerization parameters upon monomer modification. As an alternative, functionalities can be incorporated into well-defined polymer backbones after polymerization by coupling a side chain modifier with tethered reactive sites (Shenhar et al. 2004 Carroll et al. 2005 Malkoch et al. 2005). The modification step requires a clean (i.e., free from side products) and quantitative reaction so that each site has the desired chemical structures. Otherwise it affords poor reproducibility of performance between different batches. 

The need to better control surface-initiated polymerization recently led to the development of controlled radical polymerization techniques. The trick is to keep the concentration of free radicals low in order to decrease the number of side reactions. This is achieved by introducing a dormant species in equilibrium with the active free radical. Important reactions are the living radical polymerization with 2,2,4,4-methylpiperidine N-oxide (TEMPO) [439], reversible addition fragment chain transfer (RAFT) which utilizes so-called iniferters (a word formed from initiator, chain transfer and terminator) [440], and atom transfer radical polymerization (ATRP) [441-443]. The latter forms radicals by added metal complexes as copper halogenides which exhibit reversible reduction-oxidation processes. 

Living radical polymerizations in miniemulsions have also been conducted by de Brouwer et al. using reversible addition-fragmentation chain transfer (RAFT) and nonionic surfactants [98]. The polydispersity index was usually below 1.2. The living character is further exemplified by its transformation into block copolymers. 

Reversible addition-fragmentation chain transfer (RAFT) polymerization using 2,2 -azobisisobutyronitrile and either A, A-dimethyl-5-thiobenzoylthiopropionamide or A-dimethyl-5-thiobenzoylthioacetamide as chain transfer agents has been used to prepare low polydispersity poly(A, A-dimethylacrylamide). The chain transfer agents were unusually effective in suppressing free radical termination reaction, thereby mimicking a living polymerization reaction. 

MAYADUNNE R.T.A., RIZZARDO E., CHIEF ARI J., CHONG Y.K., MOAD G., THANG S.H., Living radical polymerization with reversible addition-fragmentation chain transfer (RAFT polymerization) using dithiocarbamates as chain transfer agent. Macromolecules, (1999), 32 (21), 6977-80. 

In the field of living radical polymerization, MALDI-TOF has been highly useful for characterization of polymers prepared by nitroxide-mediated radical polymerization (NMRP) [35, 36], atom transfer radical polymerization (ATRP) [37], and reversible addition-fragmentation chain transfer polymerization (RAFT) [38, 39]. The modern MALDI-TOF-MS permits fast and accurate determination of a variety of polymer characteristics [40]. 

Using NMP [114, 115] or reversible addition-fragmentation chain transfer (RAFT) [ 119,120,127], agents with ammonium groups for the ion exchange allowed the attachment of initiators on the clay surface for controlled radical polymerizations (NMP, RAFT). Samakande et al. investigated the kinetics of RAFT-mediated living polymerization of styrene [120] and styrene/BA [119] mixtures in miniemulsion. 

Anionic and later cationic pol3Tnerization gave most of examples of living pol3rmerization systems until recently, when more sophisticated methods of manipulation with free-radical polymerization processes become available. These methods are based on the use of the compounds which reversibly react with propagating radical and convert it to the so-called dormant species . When the equilibrium between the active and dormant species is regulated by special catalysts based on a transition metal, this process is called atom transfer radical polymerization (ATRP). If this equilibrium is provided by stable radicals such as nitroxides, the process is called stable free-radical polymerization (SFRP). In the case when dormant species are formed via a chain transfer rather than reversible termination reactions, this process is referred to as reversible addition fragmentation chain transfer (RAFT) polymerization. All these techniques allow to produce macromolecules of desired architecture and molecular masses. 

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