Synthesis and characterization of organic-inorganic hybrid block copolymers containing a fully condensed ladder-like polyphenylsilsesquioxane

A series of inorganicorganic hybrid block copolymers were synthesized via atom transfer radical polymerization using a fully condensed, ladder-like structured polyphenylsilsesquioxane end-functionalized macroinitiator. The inorganic portion, ladder-like polyphenylsilsesquioxane, was synthesized in a one-batch, base-catalyzed system, whereas organic hard and soft monomers, styrene, and n-butyl acrylate, were polymerized and copolymerized on the ends of the linear, inorganic backbone. Synthesized hybrid diblock, triblock, and random copolymers were characterized by 1H NMR, 29Si NMR, gel permeation chromatography, static light scattering, Fourier transform infrared spectroscopy, thermogravimetric analysis, and differential scanning calorimetry. Hybrid block copolymers were well-defined with low polydispersity (<1.4) and exhibited enhanced thermal properties in the form of increased glass transition and degradation onset temperatures over their organic analogues.(c) 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012