Abstract
The chemistry and kinetics of various elementary reactions in the cationic polymerization of styrene, including propagation, depropagation, transfer, termination, and initiation, are discussed. The limiting conditions for living systems are then estimated from a master Arrhenius plot of the rate constants of these reactions as a function of temperature. This master plot demonstrates that although polymers with DP [approximately] 7 might be prepared at 50 C, polymers with DP [approximately] 1,500 could be prepared by decreasing the temperature to [minus]70 C. The effect of solvent on the relative contribution of the different reactions is also demonstrated. New living systems are similar to classic cationic systems but with better control due to fast initiation and slower polymerization rates as a result of reversible formation of dormant species.
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