Abstract: The nanoscopic dimensions of polyhedral oligomeric silsesquioxanes (POSS) and polyhedral oligomeric silicates (POS) materials ranges from 0.7 nm to 5.0 nm and enables the thermomechanical and physical properties of polymeric materials to be improved by providing nanoscopic reinforcement of polymer chains at a length scale that is not possible by physically smaller aromatic chemical systems or larger fillers and fibers. A simple and cost effective method for incorporating POSS/POS nanoreinforcements onto polymers via the reactive grafting of suitably functionalized POSS/POS entities with polymeric systems amenable to such processes is described. The method teaches that the resulting POSS-grafted-polymers are particularly well suited for alloying agents by nongrafted POSS entitles such as molecular silicas. The successful alloying of POSS-polymers is aided because their interfacial tensions are reduced relative to non-POSS containing systems.

Abstract: Efficient processes have been developed for the cost effective functionalization of polyhedral oligomeric silsesquioxane-silanols (POSS-Silanols) and for the manufacture of polyfunctional polyhedral oligomeric silsesquioxanes. The processes utilize the action of bases or acids on silane coupling agents. The preferred process utilizes base to promote the silylation of POSS-Silanols of the formula [(RSiO1.5)n(R(HO)SiO1.0)m]?# with silane coupling agents to form POSS species with functionalized incompletely condensed nanostructures [(RSiO1.5)n(R(YSiR2O)SiO1.0)m]?# or functionalized completely condensed nanostructures [(RSiO1.5)n(YSiO1.5)1]?#. The process can alternately be conducted with acids. A second process utilizes base to alkylate POSS-Silanols with functionalized alkyl halides. A third related process utilizes base to react with silane coupling agents to form polyfunctional, fully condensed POSS species of formula [(YSiO1.5)n]?#. This process can also alternately be conducted under acidic conditions.