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Synthesis of Poly(chloromethylstyrene-b-styrene) Block Copolymers by Controlled Free-Radical Polymerization - Published online 8 September 2000 The controlled free-radical polymerization of styrene and chloromethylstyrene monomers in the presence of 2,2,6,6-tetramethyl- 1-piperidinyloxyl (TEMPO) has been studied with the aim of synthesizing block copolymers with well-defined structures. Unexpectedly, for chloromethylstyrene the rate of the TEMPO-mediated polymerization was higher than the rate of the thermal self-initiated polymerization. The kinetic modeling of the block copolymerization was in good agreement with experimental data. The block copolymers obtained in this work exhibited a low polydispersity index (weight-average molecular weight/number-average molecular weight < 1.5) and could be chemically modified with nucleophilic substitution reactions on the benzylic site, opening the way to a great variety of architectures./
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