Tg (glass transition temperature) is where it becomes floppy, and also tends to age rapidly (turn brown -- not necessarily becoming weak or brittle in the process, but getting there). There's also a lot of expansion associated with that, which would be undesirable for temp cycling.
100C ambient isn't a problem, but how much temp rise is your circuit designed for, on top of that ambient?
You can also try to keep the PCB cool by blowing air over it, clamping it between thermal pads, potting, and so on.
Tim