An efficient approach to surface-initiated ring-opening metathesis polymerization of cyclooctadiene.

Surface-initiated ring-opening metathesis polymerization of cyclooctadiene (COD), a low ring-strain olefin, is reported for the first time. Polymerization was carried out in the vapor phase, which is advantageous compared to conventional solution methods in terms of minimizing chain transfer by reducing polymer chain mobility at the vapor/solid interface. Attachments of a norbornenyl-containing silane and a Grubbs catalyst to silicon substrates were carried out before samples were exposed to COD vapor. The thickness of grafted 1,4-polybutadiene films was controlled by reaction time and reached approximately 40 nm after 7 h. The polymer films were further chemically modified to afford a new polymer, head-to-head poly(vinyl alcohol).