"Click" coupling of block copolymers prepared by ATRP

POLY 124

Patricia L. Golas, pgolas@andrew.cmu.edu, Nicolay Tsarevsky, and Krzysztof Matyjaszewski, km3b@andrew.cmu.edu. Department of Chemistry, Carnegie Mellon University, 4400 Fifth Avenue, Pittsburgh, PA 15213
The step-growth click coupling of well-defined block copolymers synthesized by atom transfer radical polymerization (ATRP) was used to prepare multisegmented block copolymers. α,ω-Diazido-terminated polystyrene-b-poly(ethylene oxide)-b-polystyrene was coupled with propargyl ether in DMF in the presence of a CuBr/N,N,N′,N′′,N′′-pentamethyldiethylenetriamine (PMDETA) catalyst. Additional multisegmented materials were prepared by click coupling of propargyl ether with another diazido-terminated triblock copolymer, poly(n-butyl acrylate)-b-poly(methyl methacrylate)-b-poly(n-butyl acrylate), and a diazido-terminated pentablock copolymer, polystyrene-b-poly(n-butyl acrylate)-b-poly(methyl methacrylate)-b-poly(n-butyl acrylate)-b-polystyrene. The formation of a product of higher molecular weight and broader molecular weight distribution was verified by triple-detection size exclusion chromatography. Differential scanning calorimetry and dynamic mechanical analysis revealed that the amphiphilic block copolymer behaves as a viscoelastic fluid, while its corresponding multiblock copolymer is an elastic material. The multisegmented block copolymers with partially miscible segments exhibit higher glass transition temperatures than their precursors.