Application of hyperbranched block copolymers as templates for the generation of nanoporous organosilicates

Abstract

A general route to organic-inorganic hybrids with nanophase morphologies has been elaborated with the objective of ultimately generating nanoporosity in organosilicates. Hyperbranched block copolymers prepared by either the sequential or concurrent polymerization of an ABC monomer (γ-(ε-caprolactone) 2-bromo-2-dimethylpropionate) with a BCD monomer (2-hydroxyethyl methacrylate) were used as the macromolecular templates. The two monomers, each polymerizing by different chemistries, for example ring-opening polymerization and atom transfer radical polymerization, bear initiating centres that are targeted for the functionality located on the accompanying monomer. Consequentially, a branched polymer is obtained which avoids the traditional multistep procedures. The branching density was altered simply by the addition of the appropriate AB (ε-caprolactone) and/or CD (methyl methacrylate) comonomers. These polymers were readily soluble initially in the organosilicate prepolymer (methyl silsesquioxane), however, upon the onset of crosslinking, both the solubility parameters and molecular weight of the organosilicate (polymethylsilsesquioxane) change, causing the hyperbranched polymer to phase separate by a nucleation and growth process. The organic polymer was selectively removed by thermolysis, producing a nanoporous inorganic structure. The size and shape of the pores are identical to those of the initial hybrid morphology. A significant reduction in the dielectric constant was achieved by simply replacing a portion of the glass matrix with air, which has a dielectric constant of 1.0.