Langmuir-Blodgett mono- and multilayers of (di)alkoxy-substituted poly(p-phenylenevinylene) precursor polymers. 2. Stability, transfer, and multilayer structure of (di)alkoxy-substituted precursor PPVs

The Langmuir monolayer stability and transfer properties of (di)alkoxy-substituted precursor PPVs were studied. All polymers formed stable monolayers, but the packing of the monomeric units in the monolayer depended strongly on the substituents. The less closely packed monolayers can be transferred with the Langmuir-Blodgett technique, while the closely packed monolayers, with strong pi-pi interaction between the aromatic rings, can only be transferred with the Langmuir-Schaefer technique due to the stiffness of the monolayers. Transmission and grazing incidence reflection FT-IR spectroscopy in combination with IR spectra computer simulations revealed that in many instances the orientation of the precursor at the water interface is largely preserved after transfer of the monolayer. The roughness and the thickness of the multilayers were determined by small-angle X-ray reflection

Langmuir-Blodgett Mono- and Multilayers of (Di)alkoxy-Substituted Poly(p-phenylenevinylene) Precursor Polymers. 1. Langmuir Monolayers of Homo- and Copolymers of (Di)alkoxy-Substituted Precursor PPVs

The Langmuir monolayer behavior of (di)alkoxy-substituted precursor poly(p-phenylenevinylenes) (PPVs) with a methoxy-leaving group was studied. The average orientation of the aromatic ring and the ether groups at the air-water interface was elucidated by external FT-infrared reflection spectroscopy measurements at the air-water interface combined with FT-IR computer simulations. The aromatic rings of the precursors, except those of the dibutoxy-substituted one, take on, directly after spreading, an almost perpendicular orientation to the water subphase. The isotherms of these precursors showed no special transitions, and these polymers can be considered to be in a condensed or 2-D collapsed state with lateral cohesive π-π interactions between the aromatic rings as the most prominent interaction leading to this condensed state. The aromatic rings of the dibutoxy-substituted precursor are lying flat at the water surface at large areas per repeating unit and can be considered to be in the expanded state directly after spreading. The isotherm of this precursor showed two transitions because here the chain conformation is predominantly determined by the butyl chains and not by the main chain.