Templating Organosilicate Vitrification Using Unimolecular Self Organizing Polymers: Evolution of Morphology and Nanoporosity Development with Network Formation

Abstract

Star-shaped polymers with a compatibilizing outer corona were dispersed into a thermosetting organosilicate matrix and used to create a nanoporous material. These environmentally responsive copolymers create nano-sized domains through a matrix-mediated collapse of the interior core of the core-corona polymeric structure. This approach relies on the outer corona of the star to compatibilize the insoluble core with the thermosetting resin and prevent aggregation such that these individual molecules template the crosslinking of the matrix and ultimately generate a single hole. The organic polymer was selectively thermalized leaving behind its latent image in the matrix with a pore size that reflected the size of the polymer molecule, and provided the expected reduction in dielectric constant. The morphology development as a function of arm number, molecular weight and volume fraction in mixtures with organosilicates as a function of cure/network conversion was investigated by SAXS, SANS, DMA, TEM and FE-SEM measurements. Amphiphilic star-shaped polymers of various block lengths and arm number, prepared by tandem controlled ring-opening polymerization (ROP) and atom transfer radical polymerization (ATRP) from dendritic initiators, were further tailored to facilitate contrast enhancement for various measurements by the incorporation of either ferrocenyl units or deuterated monomers. The pore sizes achieved by the star and dendrimer-like star macromolecular architectures range from {approx}7 to 40nm, depending on the molecular weight and architecture.