It is worthy to note that due to the multiple reactive sites of the multivinyl monomers, plenty of unreacted pendent vinyl groups are introduced to linear primary polymer chains. These pendent vinyl groups have the potential to react with propagating active centres either from their own polymer chain or others. Therefore, both of the intramolecular cyclization and intermolecular crosslinking might occur in this process.
Using the deactivation enhanced strategy, a relatively small instantaneous kinetic chain length limits the number of vinyl groups that can be added to a propagating chain end during each activation/deactivation cycles and thus keeps the polymer chains growing in a limited space. In this way, unlike what happens in free radical polymerization (FRP), the formation of huge polymer chains and large-scale combinations at early reaction stages is avoided. Therefore, a small instantaneous kinetic chain length is the prerequisite for further manipulation of intramolecular cyclization or intermolecular crosslinking. Based on the small instantaneous kinetic chain length, regulation of different chain dimensions and concentrations would lead to distinct reaction types. A low ratio of initiator to monomer would result in the formation of longer chains but of a lower chain concentration, This scenario would no doubt increases the chances of intramolecular cyclization due to the high local/spatial vinyl concentration within the growth boundary. Although the opportunity for intermolecular reactions can increase as the polymer chains grow, the likelihood of this occurring at the early stage of reactions is minimal due to the low chain concentration, which is why single chain cyclized/knotted polymers can form. However, in contrast, a high initiator concentration not only diminishes the chain dimension during the linear-growth phase thus suppressing the intramolecular cyclization, but it also increases the chain concentration within the system so that pendent vinyl groups in one chain are more likely to fall into the growth boundary of another chain. Once the monomers are converted to short chains, the intermolecular combination increases and allows the formation of hyperbranched structures with a high density of branching and vinyl functional groups.