Reversible deactivation propagation kinetics

In binary catalysts two types of propagation centers can be kinetically identified stereospecific CJ and non stereospecific C. The aluminum alkyl causes the formation of such centers by means of irreversible alkylation reactions of the corresponding S and SA sites. Moreover, it brings about the reversible deactivation of the propagation species, which is preferential for the non-stereospecific centers. The external base, in equilibrium and competition with the organoaluminum, would reversibly poison the non-stereospecific centers and, to a much lower degree, also the stereospecific centers. In the ternary catalysts a further stereospecific center, would be present. This center is most likely, but not necessarily, donor associated. In this case the aluminum alkyl, besides deactivating the various active centers to different... 

As mentioned above, the term controlled radical polymerization is sometimes used to describe a radical or ionic polymerization in which reversible deactivation of the chain carriers is an essential component of the mechanism. It increases the time of propagation, securing control of one or more kinetic features of the polymerization or one or more structural aspects of the macromolecules, or both. The adjective... 

Investigations of CROP of cyclic ethers (mainly THE) provided the first thoroughly studied examples of polymerization with reversible deactivation of growing species involving equilibria between ionic and covalent (dormant) species. Studies of polymerization kinetics led to determination of rate constants of elementary reactions and in several cases equal reactivity of ions and ion-pairs in propagation was observed, which seems to be a general phenomenon in CROP of heterocyclic monomers. 

Living polymerization is defined as chain polymerization in which chain termination and irreversible chain transfer are absent. The rate of chain initiation is usually larger than the rate of chain propagation with the result that the number of kinetic-chain carriers is essentially constant throughout the reaction. Reversible (temporary) deactivation of active centers can take place in a living polymerization, and all the macromolecules formed possess the potential for further growth. The term controlled polymerization, on the other hand, indicates control of a certain kinetic feature of a polymerization or structural aspect of the polymer. ... 

---