The construction of complex polymer architectures with well-defined topology, composition and functionality has been extensively explored as the molecular basis for the development of modern polymer materials. The unique reaction kinetics of free-radical polymerization leads to the concurrent formation of crosslinks between polymer chains and rings within an individual chain and, thus, free-radical (co)polymerization of multivinyl monomers provides a facile method to manipulate chain topology and functionality. Regulating the relative contribution of these intermolecular and intramolecular chain-propagation reactions is the key to the construction of architecturally complex polymers. This can be achieved through the design of new monomers or by spatially or kinetically controlling crosslinking reactions. These mechanisms enable the synthesis of various polymer architectures, including linear, cyclized, branched and star polymer chains, as well as crosslinked networks. In this Review, we highlight some of the contemporary experimental strategies to prepare complex polymer architectures using radical polymerization of multivinyl monomers. We also examine the recent development of characterization techniques for sub-chain connections in such complex macromolecules. Finally, we discuss how these crosslinking reactions have been engineered to generate advanced polymer materials for use in a variety of biomedical applications.
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