This review has summarized the information available in the literature regarding various copolymers that involved some aspect of controlled/living radical polymerization (CRP) for their synthesis. The topics addressed included the formation of statistical, periodic and gradient copolymers, block and graft copolymers, including tethered copolymers, and segmented polymers with star-type chain architectures. There are numerous examples of the synthesis of all of these types of copolymers using only CRP techniques, whether it is the use of nitroxide-mediated systems, ATRP, or the degenerative transfer approach. In addition, other polymerization methods have been combined with CRP to afford segmented copolymers whose compositional combinations were never before possible. Living carbocationic, carbanionic, various types of ring-opening polymerization, coordination polymerization, and even step-growth processes have all been used in conjunction with CRP methods to produce polymers with novel structures. Finally, one of the most unique approaches to the preparation of segmented copolymers has been the development of initiators and monomers that can be used for two types of polymerization processes, whether it be in a stepwise or concurrent manner. These types of advances lend themselves to the development of routes for the preparation of materials with properties that can be specifically tuned for particular applications.
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