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From the Gila website:
Can I put window film on plexiglass?
a. Plexiglass, acrylic, and lexan are three non-glass materials used to make skylights, sidelights on front doors, storm door panes, and garage door windows. The advantage of these "plastic? materials is that they are more impact-resistant than glass. They are often more durable in certain window locations than glass.
b. Window film adhesive is not designed for these "plastic" windows. Changes in temperature cause natural expansion and contraction of both plexiglass and window film. The plexiglass and the film expand and contract at different rates, which causes the film to buckle and lift off the glass.
c. If you want to reflect more heat, you may cut a piece of Heat Control film to the size and shape of the window. Leave the clear liner on the film, and mount the outside of the curl of the film onto the glass after you put a ¼" border of double-sided tape around the inside perimeter of the window.
d. Do not try to apply film to compound-curved or domed skylights. Window film will not stretch to conform to these 3-D surfaces; but it can crease, pucker, and wrinkle badly if you try to force it to fit.