Reversible-deactivation radical polymerization

Reversible deactivation radical polymerizations are members of the class of reversible deactivation polymerizations which exhibit much of the character of living polymerizations, but cannot be categorized as such as they are not without chain transfer or chain termination reactions. Several different names have been used in literature, which are:

Though the term "living" radical polymerization was used in early days, it has been discouraged by IUPAC, because radical polymerization cannot be a truly living process due to unavoidable termination reactions between two radicals. The commonly used term controlled radical polymerization is permitted, but reversible-deactivated radical polymerization or controlled reversible-deactivation radical polymerization (RDRP) is recommended.

RDRP – sometimes misleadingly called 'free' radical polymerization – is one of the most widely used polymerization processes since it can be applied

The steady-state concentration of the growing polymer chains is 10⁻⁷ M by order of magnitude, and the average life time of an individual polymer radical before termination is about 5–10 s. A drawback of the conventional radical polymerization is the limited control of chain architecture, molecular weight distribution, and composition. In the late 20th century it was observed that when certain components were added to systems polymerizing by a chain mechanism they are able to react reversibly with the (radical) chain carriers, putting them temporarily into a 'dormant' state. This had the effect of prolonging the lifetime of the growing polymer chains (see above) to values comparable with the duration of the experiment. At any instant most of the radicals are in the inactive (dormant) state, however, they are not irreversibly terminated (‘dead’). Only a small fraction of them are active (growing), yet with a fast rate of interconversion of active and dormant forms, faster than the growth rate, the same probability of growth is ensured for all chains, i.e., on average, all chains are growing at the same rate. Consequently, rather than a most probable distribution, the molecular masses (degrees of polymerization) assume a much narrower Poisson distribution, and a lower dispersity prevails.

IUPAC also recognizes the alternative name, ‘controlled reversible-deactivation radical polymerization’ as acceptable, "provided the controlled context is specified, which in this instance comprises molecular mass and molecular mass distribution." These types of radical polymerizations are not necessarily ‘living’ polymerizations, since chain termination reactions are not precluded".

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