Well, I don't think you have to worry about styrofoams flash point since it is well above 300 deg C (
Link).
But I would avoid it simply because it softens around 60-90 deg C (depending on grade) and the foam would probably collapse.
A lot of people struggle with this adhesive backing and most around here seem to prefer to not use it all together for the very reason you have encountered (it doesn't come off). Of course, everything works fine without the adhesive except that you usually need to eother take the motherboard out of the case or have access slots in the motherboard tray every time you want to reinstall the HSF.
If you're interested in a little tinkering,
here is a thread I saw recently that describes a way to use cardboard instead.