Controlled/living radical degenerative transfer

The fifty chapters submitted for publication in the ACS Symposium series could not fit into one volume and therefore we decided to split them into two volumes. In order to balance the size of each volume we did not divide the chapters into volumes related to mechanisms and materials but rather to those related to atom transfer radical polymerization (ATRP) and to other controlled/living radical polymerization methods reversible-addition fragmentation transfer (RAFT) and other degenerative transfer techniques, as well as stable free radical pol5mierizations (SFRP) including nitroxide mediated polymerization (NMP) and organometallic mediated radical polymerization (OMRP). 

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. 

Atom Transfer Radical Polymerization. ATRP is one of the most successful controlled/living radical polymerization (CRP) systems, in addition to NMP and degenerative transfer processes, such as RAFT (5,233,234). The key feature of all of them is the dynamic equilibration between the active radicals and varions tsqjes of dormant species (see Living Radical Polymerization). 

If an overall conclusion could be made, it might be considered that the counterradicals vary considerably (Scheme 3). They can either be stable (e.g., nitroxyls, arylazooxyls), semi persistent (e.g., from thiourams) and also metallic (e.g., acetoacetato metals). In addition, if these radicals either terminate or transfer, non-living (or inactive) species will be produced. But, in order to preserve the living character, the radicals must propagate and in specific cases (e.g., iodine transfer polymerization or degenerative transfer) active species will be obtained. The more that one of these latter steps is favored, the more living is the tendency of the radical polymerization, with a very high kinetic control of this reaction. 

Control by degenerative transfer (DT) involves perhaps the smallest change from a eonventional free radical process of all the controlled/living polymerization proeesses developed to date. A recent review of various methods of telomer synthesis [180] diseusses the different types of transfer agents and monomers and the contribution of the teehniques of telomerization to CRP (includes discussion of iodine transfer polymerization, RAFT, and macromolecular design through interchange of xanthates (MADIX)) [181,182]. 

Substantial effort has been directed toward the control of vinyl acetate (VAc) radical polymerization using living radical polymerization (LRP) methods, including atom transfer radical polymerization, degenerative transfer through alkyl iodide,dialkyl tellurium, trithiocarbonate, xanthate, and cobalt acetylacetonate The focus of... 

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