Step-growth polymer from thermal

Babb, D. A. Snelgrove, R. V. Smith, D. W., Jr. Mudrich, S. F. Novel Step-Growth Polymers from the Thermal (2p - -2pj Cyclopolymerization of Aryl Trifluorovinyl Ether Monomers-, ACS Symposium Series ACS Publications, 1996 pp 431 41. 

The control of the polymerization reaction afforded by ATRP is the result of the formation of dormant alkyl (pseudo)halides. This reduces the instantaneous concentration of the active radicals and thereby suppresses bimolecular termination reactions. The reversible deactivation and activation leads to a slow, but steady growth of the polymer chain with a well defined end group (Scheme 27). Control and properties of the synthesized polymers depend on the stationary concentration of active radicals and the relative rates of propagation and deactivation. When one or less than one monomer unit is incorporated into the polymer chain during one activation step, the polymerization is well controlled. The ATRP equilibrium can be approached from both directions in Scheme 27. Beginning with an alkyl halide and the lower valent metal complex, the process is called direct ATRP. If a conventional thermal initiator like AIBN and the higher valent metal complex are the starting materials, the polymerization process is named reverse ATRP [287]. 

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