The regioselective monohydrosilation of α,ω-hydrogen-functional oligodimethylsiloxanes has been used to prepare a series of well-characterized a-hydrogen-ω-epoxy functional oligodimethylsiloxanes. Using these latter compounds as substrates, a wide variety of interesting cationically polymerizable monomers can be prepared a) by further hydrosilation b) oxidative coupling and b) by reaction with vinyl functional photosensitizers. These monomers possess outstanding reactivity. The reactivities of the new monomers and oligomers were examined using Fourier transform realtime infrared spectroscopy and optical pyrometry. Those monomers containing epoxycyclohexyl groups displayed excellent reactivity in cationic ring-opening polymerization in the presence of lipophilic onium salts photoinitiators.
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