Surface initiation from adsorbed polymer clusters: a rapid route to superhydrophobic coatings.

We introduce the use of a hydroborated polyisoprene (PIP) macroinitiator for the rapid surface-initiated growth of superhydrophobic polymethylene (PM) films. Rinsing of a dip-coated PIP film on a methyl-terminated surface atop silicon or gold substrates results in robustly bound, isolated PIP clusters. After hydroboration of the internal olefins, these clusters result in extremely rapid growth of polymethylene coatings upon exposure to a diazomethane solution in diethyl ether at -17 °C. The resulting PM films achieve 6 μm thicknesses within 20 min of polymerization and become superhydrophobic with advancing and receding water contact angles of 166° and 156°, respectively, within 1 min. The PM films grown from these PIP clusters exhibit 3× greater propagation velocities, 30% lower termination rates, and more highly textured morphologies than PM films grown from hydroborated monolayers.