Chemical and Photochemical Dual Polymerization in a Mixed Langmuir Monolayer of Diacetylene Derivatives and Octadecyltrimethoxysilane.

A chemical-and-photochemical-induced dual polymerization at the air-water interface was performed for the first time, by using a ternary mixture of a octadecyltrimethoxysilane (C18TMS), 10,12-pentacosadiynoic acid (PDA), and N-(11-O-alpha-d-mannopyranosyl-3,6,9-trioxa) undecyl 10,12-pentacosa-diynamide (PDTM). Different dual polymerization behaviors of the mixed monolayers of PDA/PDTM/C18TMS (7:1:8 molar ratio) at different subphase pH were monitored by surface pressure-area isotherms and UV-vis spectra. At pH 1, the C18TMS formed a long linear polymer network by strong intermolecular condensation. The PDA/PDTM was isolated to small domains by this network and can only be polymerized weakly upon UV irradiation. At pH 2.6, the weak condensation of C18TMS formed short linear polymers, which caused phase separation between C18TMS and PDA/PDTM. The strong photochemical polymerization of the PDA/PDTM rich domain was similar to the PDA/PDTM binary mixed monolayer. At pH 4.0, the partially hydrolyzed C18TMS was miscible with PDA/PDTM and slowed the polymerization process of PDA/PDTM upon UV irradiation. These results show geometry and kinetic controls of the PDA/PDTM polymer in 2D by using the C18TMS polymer network. Copyright 1998 Academic Press.