A facile and general method for the preparation of chemically responsive

polymer films is demonstrated. First, a crosslinked polymer precoating

layer is created via self-initiated photografting and

photopolymerization of ethylene glycol dimethacrylate on a

self-assembled monolayer of a 3-(trimethoxysilyl)propylamine modified

oxidized silicon wafer. The intact methacrylate functionalities are used

to grow polymer chains by a second self-initiated photografting and

photopolymerization of vinyl monomers to form polymer brushes on the

crosslinked layer; thus a series of polymer membranes of PMMA, PDMAEMA

and P4VP are obtained. The double-layered polymer membranes can be

lifted off via hydrofluoric acid etching of the oxidized

silicon layer to give integral free-standing polymer membranes. Kinetic

studies revealed that the thickness of both the crosslinked precoating

layer and the brush layer increased linearly as a function of the

polymerization time before the reaction solutions got highly viscous.

Furthermore, polyoxometalate Na9(EuW10O36)

can be uniformly incorporated into the PDMAEMA membrane through

electrostatic interactions to afford an acid/base gas-responsive

luminescent hybrid film.