Processes have been developed for the manufacture of polyhedral oligomeric
silsesquioxanes (POSS), polysilsesquioxanes, polyhedral oligomeric silicates (POS),
and siloxane molecules bearing reactive ring-strained cyclic olefins (e.g. norbornenyl,
cyclopentenyl, etc. functionalities). The preferred manufacturing processes employ
the silation of siloxides (Si-OA, where A=H, alkaline or alkaline earth metals)
with silane reagents that contain at least one reactive ring-strained cyclic olefin
functionality [e.g., X3-ySi(CH3)y(CH2)2
where y=1-2 and X=OH, Cl, Br, I, alkoxide OR, acetate OOCR, peroxide OOR, amine
NR2, isocyanate NCO, and R]. Alternatively, similar products can be
prepared through hydrosilation reactions between silanes containing at least one
silicon-hydrogen bond (Si-H) with ring-strained cyclic olefin reagents [e.g., 5-vinyl,
2 norbornene CH2CH, cyclopentadiene]. The two processes can
be effectively practiced using polymeric silsesquioxanes [RSiO1.5]
where =1-1,000,000 or higher and which contain unreacted silanol or silane
groups at chain terminus or branch points, on POSS nanostructures of formulas [(RSiO1.5)n]#,
homoleptic, [(RSiO1.5)m(RSiO1.5)n]#,
heteroleptic, and {(RSiO1.5)m(RXSiO1.0)n}#,
functionalized heteroleptic nanostructures, on silanes RSiX3, linear,
cyclic, oligomeric and polymeric siloxanes (polymeric formula RX2Si-(OSiRX)m-OSiRX2
where m=0-1000, X=OH, Cl, Br, I, alkoxide OR, acetate OOCR, peroxide OOR,
amine NR2, isocyanate NCO, and R). Each of the processes result in new
chemical species bearing one or more ring strained olefins that can undergo polymerization,
grafting, or other desirable chemical reactions to form polymeric products. These
polymeric systems are most desirably utilized in polymerizations for the modification
of properties of thermoplastic or thermoset resin systems or for the preparation
of polymers with utility in electronics, medical devices, sporting goods, and aerospace
as coatings and structural components.
