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The following section on nano-composites formed by grafting from the surface of a functionalized particle is an evolution of the "core first" approach to synthesis of star macromolecules. Initially a low molecular weight multi-functional molecule was used in a "grafting from" reaction to form star macromolecules with a well defined number of arms. Use of hexakis(chloromethyl)benzene as a well defined multifunctional initiator for the polymerization of styrene provided the first multi-arm polymer prepared using ATRP.(5,7) The composition of the core and arms were quickly expanded.(7-9,32)

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A simple sequential polymerization of a crosslinker followed by polymerization of a monomer(33) provides a broadly applicable approach to star copolymers. This novel method, termed "star from in situ generated core", belongs to the broader category of "core-first" methodology and presents an alternative strategy for star synthesis when compared to the traditional "arm-first" method, in which monomer is polymerized first followed by formation of the core by (co)polymerization of a cross-linker.

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Obviously the question would not be asked in a public forum if the answer was yes. It was recently disclosed how a standard free radical polymerization can be used for the high-yield synthesis of uniform star copolymers.(38) In the paper a novel simple method was reported for the synthesis of well-defined star polymers in high star yield by applying a conventional radical polymerization procedure to the copolymerization of linear macromonomers and divinyl cross-linkers in a homogeneous solution of the reagents.

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The advantages of conventional radical polymerization for star synthesis, as compared to other polymerization techniques, include but are not limit to:

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To illustrate this new concept for the synthesis of star polymers using controlled radical polymerization techniques, ATRP was applied to the homopolymerization of a crosslinker, ethylene glycol diacrylate (EGDA) to generate a multifunctional crosslinked core (nanogel). Monovinyl monomers were added to the reaction mixture at high conversion of the crosslinker and were polymerized from the polyEGDA nanogel macroinitiator (MI) to form the star arms. A spectrum of different acrylate monomers were polymerized from the first formed core providing star polymers with different compositions for the arms.

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We recently reported a new strategy for synthesis of miktoarm star copolymers using a simple and general "arm-first" method, i.e., one-pot ATRP cross-linking a mixture of different linear MIs and/or MMs with a divinyl cross-linker in order to synthesize miktoarm star copolymers with potentially any desired molar ratio and composition of the arms.(35,37)